Fabrication fluids

ABSTRACT

A fabrication fluid composition, such as a metal cutting fluid concentrate, contains water, a first surfactant which is an anionic surfactant, a second surfactant which is an amphoteric surfactant, a third surfactant which is selected from an anionic surfactant and an amphoteric surfactant, the third surfactant being different from the first and second surfactants, and water, along with at least one of an anti-rust agent, a coloring agent, and a de-foaming agent. The concentrate may be combined with water to provide a fabrication fluid such as a metal cutting fluid composition that may be applied to a piece of metal being cut for a time and in an amount effective to dissipate heat from the metal being cut.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit under 35 U.S.C. § 119(e) of U.S.Provisional Patent Application No. 62/570,617 filed Oct. 10, 2017, whichapplication is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates generally to compositions for fabricatingmaterials where heat is generated (e.g., the cutting of metal or stone),concentrates thereof, and methods of making and using the compositions.

BACKGROUND

During the process of fabricating (e.g., cutting) solid materials suchas stone or metal (e.g., drilling a hole in metal or cutting a piece ofmetal into smaller pieces), fluids are typically utilized to lubricatethe cutting or shaping device in order to lessen wear and tear on thedevice involved in fabrication. The fluid, e.g., metal cutting fluid, isapplied at the location where the material, e.g., metal, is being cut bythe cutting device, e.g., a blade. The fluid provides various functions,including helping to dissipate the heat that is generated during thefabricating process, e.g., the cutting action. Absent dissipation, theheat can cause warpage and/or other damage to one or both of the cuttingdevice and the material, e.g., metal, that is being cut. Other advantageof fabrication fluids include enhancing tool life, improving surfacefinish, and flushing away chips from the cutting zone. Practically allcutting fluids presently in use fall into one of four categories: 1)straight oils, 2) soluble oils, 3) semisynthetic fluids, and 4)synthetic fluids.

Straight oils are non-emulsifiable and are used in machining operationsin an undiluted form. They are composed of a base mineral or petroleumoil and often contains polar lubricants such as fats, vegetable oils andesters as well as extreme pressure additives such as chlorine, sulphurand phosphorus. Straight oils provide the best lubrication and thepoorest cooling characteristics among cutting fluids.

Soluble oil fluids form an emulsion when mixed with water. Theconcentrate consists of a base mineral oil and emulsifiers to helpproduce a stable emulsion. They are used in a diluted form (usualconcentration=3 to 10%) and provide good lubrication and heat transferperformance. They are widely used in industry and are the leastexpensive among all cutting fluids.

Semi-synthetic fluids are essentially combination of synthetic andsoluble oil fluids and have characteristics common to both types. Thecost and heat transfer performance of semi-synthetic fluids lie betweenthose of synthetic and soluble oil fluids.

Synthetic fluids contain no petroleum or mineral oil base and insteadare formulated from alkaline inorganic and organic compounds along withadditives for corrosion inhibition. They are generally used in a dilutedform (usual concentration is 3 to 10%). Synthetic fluids often providethe best cooling performance among all cutting fluids and the poorestlubricating characteristics among cutting fluids.

There is a need for improved fabrication fluids, e.g., improved metalcutting fluids. The present disclosure is directed to fulfilling thisneed.

SUMMARY

Briefly stated, the present disclosure provides fabricating fluidconcentrates, e.g., metal cutting, fabricating fluid compositions, e.g.,metal cutting fluids, which are diluted forms of the concentrates,methods of making the concentrates and the compositions, and methods ofusing the concentrates and the compositions in material fabricationprocesses, e.g., in order to cut metal, stone, plastic, etc.

In one embodiment, the present disclosure provides a compositioncomprising water and non-volatile components (also referred to herein assolids, even though some of the non-volatile components may be, in apure state, liquids). The solids include one or more surfactants, whereexemplary surfactants are anionic surfactants and amphotericsurfactants. For example, the solids may include a first surfactantselected from amphoteric surfactants, a second surfactant selected fromanionic surfactants, and a third surfactant selected from an amphotericand an anionic surfactant, the third surfactant being different from thefirst and second surfactants. The solids also include one or more agentsselected from anti-rust and anti-corrosion agents, which will bereferred to herein collectively as anti-rust agents.

Optional non-volatile components present in the composition include oneor more of a thickener, also referred to as a thickening agent, which issuitable for increasing the viscosity or body of the composition; aninorganic salt which is water soluble at the concentration utilized inthe composition; an organic solvent which is miscible with water at theconcentration utilized in the composition; a de-foaming agent, whichterm includes anti-foaming agents, which is used in an amount effectiveto mitigate foaming of the composition during use; and a coloring agent,also referred to herein as a colorant, that imparts coloration to thecomposition.

As mentioned previously, the compositions of the present disclosureinclude water in addition to the non-aqueous ingredients which arenon-volatile. In one embodiment, the composition contains relativelylittle water, so that the composition has a high concentration ofnon-volatile components. Such a composition may be referred to herein asa concentrate (or concentrated) composition, or a metal cuttingconcentrate. The concentrate may be provided to facilities that cutmetal or otherwise fabricate materials, where the operators in thosefacilities may dilute the concentrate with an amount of water thatprovides a fluid having suitable properties for the particularfabrication situation, e.g., cutting metal or other material. Forexample, cutting bronze may benefit from a different dilution of theconcentrate than is utilized for cutting a different metal, such asstainless steel. In one embodiment, the concentrate is 5-50% by weightof water. In another embodiment, the concentrated composition is 40-50%by weight water, and 50-60% by weight of non-aqueous components,including a surfactant, an anti-rust agent, and at least one of athickening agent suitable for an aqueous composition, and an inorganicsalt. In another embodiment, the present disclosure provides metalcutting fluids that are ready-to-use in a metal cutting operation. Insuch ready-to-use compositions, the water content will typically be inthe range of 75-99% by weight, or 75.0-99.9% by weight, or 90-99% byweight water, or 90.0-99.9% by weight water, or 97.0-99.9 wt % water, or98.0-99.9 wt % water, or 99.0-99.9 wt % water.

In one embodiment, the composition comprises water, a first surfactantselected from amphoteric surfactants, a second surfactant selected fromanionic surfactants, a third surfactant selected from an amphoteric andan anionic surfactant, the third surfactant being different from thefirst and second surfactants, an inorganic salt, an organic solvent, athickening agent, an anti-rust agent, and a de-foaming agent.

The following numbered embodiments are additional exemplary embodimentsof the compositions of the present disclosure:

-   -   1) A fabricating fluid composition comprising water, a first        surfactant, a thickening agent, and an anti-rust agent.    -   2) A fabricating fluid composition comprising water, a first        surfactant, an inorganic salt, and an anti-rust agent.    -   3) A composition of embodiments 1 or 2 wherein the first        surfactant is an anionic surfactant.    -   4) A composition of embodiment 3 wherein the first surfactant is        an anionic surfactant comprising a sulfonate group or comprising        a sulfate group.    -   5) A composition embodiment 3 wherein the first surfactant is        sodium dodecylbenzene sulfonate.    -   6) A composition of embodiment 3 wherein the first surfactant is        sodium laureth sulfate.    -   7) A composition of embodiments 1 or 2 wherein the first        surfactant is an amphoteric surfactant.    -   8) A composition of embodiment 7 wherein the amphoteric        surfactant comprises a betaine group.    -   9) A composition embodiment 7 wherein the first surfactant is        cocamidopropyl betaine.    -   10) A composition of embodiments 1 or 2 comprising two        surfactants, each of the two surfactants being an anionic        surfactant.    -   11) A composition of embodiment 10 wherein the two surfactants        are a sulfate-containing surfactant and a sulfonate-containing        surfactant. p1 12) A composition of embodiment 10 wherein the        two surfactants are sodium laureth sulfate and sodium        dodecylbenzene sulfonate.    -   13) A composition of embodiments 1 or 2 comprising two        surfactants, one being an anionic surfactant and the other being        an amphoteric surfactant.    -   14) A composition of embodiment 13 wherein the two surfactants        are a sulfate-containing anionic surfactant and a        betaine-containing amphoteric surfactant.    -   15) A composition of embodiment 14 wherein the        sulfate-containing anionic surfactant is sodium laureth sulfate        and the betaine-containing amphoteric surfactant is        cocamidopropyl betaine.    -   16) A composition of embodiment 13 wherein the two surfactants        are a sulfonate-containing anionic surfactant and a        betaine-containing amphoteric surfactant.    -   17) A composition of embodiment 16 wherein the        sulfonate-containing anionic surfactant is sodium dodecylbenzene        sulfonate and the betaine-containing amphoteric surfactant is        cocamidopropyl betaine.    -   18) A composition of embodiments 1 or 2 comprising three        surfactants, two of the three surfactants being non-identical        anionic surfactants and one of the three surfactants being an        amphoteric surfactant.    -   19) A composition of embodiment 18 wherein the three surfactants        are a sulfate-containing surfactant, a sulfonate-containing        surfactant, and a betaine-containing surfactant.    -   20) A composition of embodiment 19 wherein the three surfactants        are sodium dodecylbenzene sulfonate, sodium laureth sulfate, and        cocamidopropyl betaine.    -   21) A composition of embodiments 1 or 2 wherein the anti-rust        agent is sodium nitrite.    -   22) A composition of embodiment 20 wherein the anti-rust agent        is sodium nitrite.    -   23) A composition of embodiments 1 or 2 comprising a thickening        agent which is a cellulosic thickening agent.    -   24) A composition of embodiment 23 wherein the cellulosic        thickening agent is hydroxyl ethyl cellulose.    -   25) A composition of embodiment 20 comprising a thickening agent        which is a cellulosic thickening agent.    -   26) A composition of embodiment 25 wherein the cellulosic        thickening agent is hydroxyl ethyl cellulose.    -   27) A composition of embodiments 1 or 2 comprising an inorganic        salt which is calcium chloride.    -   28) A composition of embodiment 20 comprising an inorganic salt.    -   29) A composition of embodiment 28 wherein the inorganic salt is        calcium chloride    -   30) A composition of embodiments 1 or 2 comprising a defoaming        agent.    -   31) A composition of embodiment 30 wherein the defoaming agent        is a silicone polymer.    -   32) A composition of embodiment 20 comprising a defoaming agent.    -   33) A composition of embodiment 32 wherein the defoaming agent        is a silicone polymer.    -   34) A composition of embodiment 20 comprising one or more of a        cellulosic thickening agent, an inorganic salt, and a defoaming        agent.    -   35) A composition of embodiment 20 comprising a cellulosic        thickening agent, an inorganic salt, and a defoaming agent.    -   36) A composition of embodiment 1 comprising water, sodium        dodecylbenzene sulfonate, sodium laureth sulfate, cocamidopropyl        betaine, a thickening agent such as a cellulosic thickening        agent, and an anti-rust agent.    -   37) A composition of embodiment 2 comprising water, sodium        dodecylbenzene sulfonate, sodium laureth sulfate, cocamidopropyl        betaine, an inorganic salt such as calcium chloride, and an        anti-rust agent.

The composition may be used for metal fabrication, and may be referredto alternatively as a metal fabrication composition, or a metal workingcomposition, or a metal cooling composition, or a metal cuttingcomposition. The composition may also be used for fabricating parts madefrom stone, plastic or glass, or other solid material that may befabricated by tooling in a heat-generating process.

In one embodiment, the present disclosure provides a method of making aconcentrated composition, e.g., a metal cutting fluid concentrate, bycombining the ingredients as discussed herein. Optionally, theingredients may be combined in a batch method. In this embodiment, acomposition, e.g., a metal cutting fluid concentrated composition isprepared by a method comprising adding to a container, hot water, one ormore surfactants such as an anionic surfactant, an amphotericsurfactant, and optionally a third surfactant selected from an anionicsurfactant and an amphoteric surfactant, where the third surfactant isdifferent from the already added anionic and amphoteric surfactants.Additional optional ingredients include an inorganic salt, an organicsolvent, a thickening agent, an anti-rust or anti-corrosion agent, acoloring agent, and a de-foaming agent; wherein after an addition of acomponent to the container, a resulting mixture is stirred until itreaches a completely or nearly homogeneous state, for example, for about30 minutes with minimal foam generation before addition of a nextcomponent. In one embodiment, an inorganic salt, an organic solvent, athickening agent, an anti-rust or anti-corrosion agent, and a de-foamingagent are added to the container.

For example, the present invention provides a process for making afabricating fluid composition, such as a composition suitable for metalcutting, comprising:

-   -   a) heating water to about 70-80° C. to provide hot water;    -   b) adding an anionic surfactant to the hot water;    -   c) adding an amphoteric surfactant to the mixture of step b);    -   d) adding hot water to the mixture of step c);    -   e) optionally adding a third surfactant to the mixture of step        d), the third surfactant selected from an anionic surfactant and        an amphoteric surfactant, the third surfactant being different        from the anionic surfactant and the amphoteric surfactant        already present in the mixture;    -   f) adding inorganic salt to the mixture of step e);    -   g) cooling the mixture of step f) to ambient temperature; and    -   h) adding thickening agent to the mixture of step f);

wherein after an addition of a component, a resulting mixture is stirredfor a time effective to achieve a homogeneous or nearly homogeneousmixture, typically about 30 minutes, with minimal foam generation beforeaddition of a next component. Exemplary optional ingredients that may beused in the process include an inorganic salt, an organic solvent, athickening agent, an anti-rust or anti-corrosion agent, a coloringagent, and a de-foaming agent. In one embodiment, an inorganic salt, anorganic solvent, a thickening agent, an anti-rust or anti-corrosionagent, and a de-foaming agent are added to the mixture.

In one embodiment, the present disclosure provides a method of making acomposition, e.g., a metal cutting fluid concentrate, by a continuousmethod. In this embodiment, a composition, e.g., a metal cutting fluidconcentrate is prepared by providing a continuous reactor, chargingwater to the continuous reactor, adding to the water in the continuousreactor a) an anionic surfactant, b) an amphoteric surfactant, andoptionally c) a third surfactant selected from an anionic surfactant anda cationic surfactant, the third surfactant being different from theanionic and amphoteric surfactant already charged to the reactor; andmixing components a), b) and optionally c) to provide a homogeneousmixture. Optionally, the water in the continuous reactor is maintainedat a temperature in excess of 50° C. Optionally, additional ingredientsare added to the formulation, such as organic solvent, inorganic salt, athickening agent, an anti-rust or anti-corrosion agent, a coloringagent, and a de-foaming agent. In one embodiment, each of an organicsolvent, inorganic salt, a thickening agent, an anti-rust oranti-corrosion agent, and a de-foaming agent are added to the mixture.Optionally, a mixer selected from an inline mixer and a static mixer ispresent in the continuous reactor.

In one embodiment, the present disclosure provides a method for forminga fabrication fluid from a precursor concentrate, e.g., a metal cuttingfluid composition from the metal cutting fluid concentrate. According tothis embodiment, water and concentrate are combined in a suitablewater:concentrate ratio, and the two components are mixed together toform the metal cutting fluid composition. In various optionalembodiments, the concentrate is diluted by a factor of 5×, or 10×, or15×. To be clear, a dilution of 5× refers to combining 100 parts ofconcentrate with 500 parts of water, where parts may be in either liquidor solid measurement forms, e.g., grams, kilograms, liters.

In one embodiment, the present disclosure provides a method for cuttingmetal, where the method comprises applying an effective amount of themetal cutting fluid composition of the present disclosure onto metalbeing cut. The metal cutting fluids of the present disclosure may beapplied to metal during the process in which the metal is being cut. Oneexemplary process for applying the compositions of the presentdisclosure is flood application, wherein a flood of cutting fluid isapplied onto the workpiece being cut. Another exemplary process forapplying the compositions of the present disclosure is jet application,wherein a jet of cutting fluid is applied onto the workpiece directed atthe cutting zone. Another exemplary process for applying the compositionof the present disclosure is mist application, wherein cutting fluid isatomized by a jet of air and the mist is directed at the cutting zone ofthe workpiece.

The following numbered embodiments are additional exemplary embodimentsof the methods of machining meal of the present disclosure, withreference to the foregoing composition embodiments:

-   -   38) A method of machining a material selected from metal, stone,        glass and plastic, comprising applying a composition comprising        a composition of any of embodiment 1-37 to a piece of material        being machined, in an amount and time that are effective to        dissipate heat from the material being machined.    -   39) The method of embodiment 38 wherein the material being        machined is metal selected from aluminum alloy, brass, casting        iron, bronze, low-carbon steel, stainless steel, alloy steel,        and titanium alloy.    -   40) The method of embodiment 38 whrein the material being        machined is stone.    -   41) The method of embodiment 38 wherein the material being        machined is glass.    -   42) The method of embodiment 38 wherein the material being        machined is plastic.    -   43) The method of embodiment 38 wherein the piece of material        being machined is being subjected to a process selected from        broaching, tapping, hobbing, cutting, drilling, milling,        turning, sawing, honing, and grinding.

The details of one or more embodiments are set forth in the descriptionbelow. The features illustrated or described in connection with oneexemplary embodiment may be combined with the features of otherembodiments. Other features, objects and advantages will be apparentfrom the description and the claims. In addition, the disclosures of allpatents and patent applications referenced herein are incorporated byreference in their entirety.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present disclosure provides a materials fabricationcomposition, such as a metal cutting fluid composition, in bothconcentrated and diluted (ready to use) form. In another aspect, thepresent disclosure provides a method of forming a fabrication fluid in aconcentrated form and then diluting that concentrated composition to adilute form. In another aspect, the present disclosure provides a methodof using the compositions in a method wherein a material is fabricated,such as a metal cutting operation. Thus, in another aspect, the presentdisclosure provides a method of forming fabricating fluid compositions,e.g., a metal cutting fluid composition, in a concentrated form and thendiluting that concentrated composition to a dilute form. In anotheraspect, the present disclosure provides a method of using thecompositions in a material cutting or shaping process, e.g., a metalcutting operation. When the present disclosure refers to a metal cuttingfluid or a metal cooling fluid, it should be understood that these fluidcomposition may be used generally in material fabrication, e.g., glassfabrication, stone fabrication, and plastic fabrication, and are notlimited in use to metal fabrication. Thus, the metal cutting or metalcooling compositions may be used for metal cutting or fabrication, butmay also be used for the fabrication of other materials such as stone orplastic or glass where fabrication generates heat that is desirablydissipated during the fabrication process.

In one embodiment, the present disclosure provides a compositioncomprising water and non-volatile components (also referred to herein assolids, even though some of the non-volatile components may be, in apure state, liquids). The solids include one or more surfactants, whereexemplary surfactants are anionic surfactants and amphotericsurfactants. For example, the solids may include a first surfactantselected from amphoteric surfactants, a second surfactant selected fromanionic surfactants, and a third surfactant selected from an amphotericand an anionic surfactant, the third surfactant being different from thefirst and second surfactants. The solids also include one or more agentsselected from anti-rust and anti-corrosion agents, which will bereferred to herein collectively as anti-rust agents.

Optional non-volatile components present in the composition include oneor more of a thickener, also referred to as a thickening agent, which issuitable for increasing the viscosity or body of the composition; aninorganic salt which is water soluble at the concentration utilized inthe composition; an organic solvent which is miscible with water at theconcentration utilized in the composition and has a boiling point abovethe boiling point of water, e.g., a boiling point of at least 125° C.,or at least 150° C., or at least 170° C.; a de-foaming agent, which termincludes anti-foaming agents, which is used in an amount effective tomitigate foaming of the composition during use; and a coloring agent,also referred to herein as a colorant, that imparts coloration to thecomposition.

In one aspect, the fluid composition contains no carbon-halogen bonds,and thus is more environmentally friendly than alternative fluidcompositions that contain one or more components having such bonds.

The fluid of the present disclosure provides the following effectsduring materials fabrication, and particularly during metal machining.Primary effects include lubricating the cutting process primarily at lowcutting speeds, cooling the workpiece primarily at high cutting speeds,and flushing chips away from the cutting zone. Secondary effects includecorrosion protection of the machined surface, and enabling part handlingby cooling the hot surface. Process effects of using cutting fluids ofthe present disclosure in machining include: longer tool life, reducedthermal deformation of workpiece, better surface finish, and ease ofchip and swarf handling.

The compositions of the present disclosure provide good heat transferperformance, good lubrication performance, good chip flushingperformance, good generation of fluid mist, good fluid carry off inchips, and good corrosion inhibition. The compositions in emulsion formexhibit good fluid stability.

It is noted that, as used in this specification and the intended claims,the singular form “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. Thus, for example, reference to“an amphoteric surfactant” includes a single amphoteric surfactant aswell as one or more of the same or different amphoteric surfactants.

Components

The compositions of the present disclosure include at least onesurfactant. In one embodiment, the compositions contain an amphotericsurfactant. In another embodiment, the compositions contain an anionicsurfactant. In one embodiment the compositions contain two differentamphoteric surfactants, optionally in combination with an anionicsurfactant. In one embodiment the compositions contain two differentanionic surfactants, optionally in combination with an amphotericsurfactant.

Amphoteric Surfactant

In one embodiment, the compositions of the present disclosure include atleast one, and optionally include more than one, amphoteric surfactant.As used herein, an amphoteric surfactant is a molecule that containsboth a positively charged atom and a negatively charged atom. Surfactantmolecules may include polymeric components, and may also include acounterion(s) such as sodium and ammonium, however the counterion is notconsidered to be one of the positively or negatively charged atoms thatqualifies the molecule as being an amphoteric surfactant.

The positively charged atom may be, for example, a nitrogen atom whichprovides, e.g., an ammonium group, or may be a sulfur atom whichprovides, e.g., a sulfonium group. The presence of a positive charge ona particular atom may be a function of the pH to which the molecule isexposed. In other words, the amphoteric surfactant of the presentdisclosure need not have a positively charged atom and a negativelycharged atom at every pH of the surrounding solution, but may have thesecharged atoms only within a pH range. For example, when the molecule hasa nitrogen atom that bears a positive charge, that charge may only bepresent when the pH of the surrounding solution (an aqueous solution) issufficiently low that the nitrogen atom becomes protonated. This occurs,for example, when the nitrogen atom is part of a primary, secondary ortertiary amine. Alternatively, the nitrogen atom may be part of aquaternary ammonium ion which maintains its positive charge regardlessof the pH of the surrounding solution.

The negatively charged atom may be, for example, an oxygen atom whichmay be part of a recognized functional group such as a carboxylate,sulfate, sulfonate, or phosphate group. As with the positive charge, thepresence of a negative charge on a particular atom may be a function ofthe pH to which the molecule is exposed. In other words, the amphotericsurfactant of the present disclosure need not have a negatively chargedatom and a positively charged atom at every pH of the surroundingsolution, but may have these charged atoms only within a pH range. Forexample, when the molecule has an oxygen atom that bears a negativecharge, that charge may only be present when the pH of the surroundingsolution (an aqueous solution) is sufficiently high that the oxygen atombecomes deprotonated. This may occur, for example, when the oxygen atomis part of, e.g., a carboxylic acid group, where only the carboxylateform of the carboxylic acid group has a negatively charged oxygen atomwhile the corresponding carboxylic acid form has a neutral oxygen atom.

In summary, the amphoteric surfactant need not have both a positivelycharged atom and a negatively charged atom throughout the entirepossible pH range of the surrounding solution, but will have these twocharged atoms at some pH range, which is sometimes referred to in theart as the isoelectric pH range. When the amphoteric surfactant has botha positively and negatively charged atom, the surfactant may be said tobe in its zwitterionic form. When a chemical structure of an amphotericsurfactant is provided herein, the term X may be used to refer to thecounterion which may be associated with the positively or negativelycharged atom within the isoelectric pH range. Exemplary cationiccounterions are sodium and ammonium. Exemplary anionic counterions arechloride and phosphate. Noteworthy is that either the positive ornegative charge may be delocalized over a plurality of atoms. Forexample, when the negative charge is on an oxygen atom, and that oxygenatom is part of a carboxylate group, the negative charge is delocalizedover both of the oxygen atoms of the carboxylate group.

In addition, and as with all surfactants, the amphoteric surfactant willhave both a lipophilic (a.k.a., hydrophobic) region and lipophobic(a.k.a., hydrophilic) region. The lipophilic region may be referred toas the fatty region. The fatty region may be composed of the hydrocarbonportion which is present in a naturally occurring fatty acid, fattyalcohol, fatty amine or the like, however it may alternatively be formedsynthetically, i.e., it may be a synthetically produced fragment such aspolyethylene, polypropylene, poly(propylene oxide), etc. As used herein,and when describing a class of amphoteric surfactant, the term

“R” will be used to refer to a fatty region of the molecule. In variousembodiments, R designates a medium or long chain fatty group, such as: aC₆-C₂₄ fragment, i.e., a molecular fragment having at least 6 and up to24 carbon atoms, and optionally any other atoms, e.g., hydrogen, halogen(e.g., F, Cl, Br), nitrogen, and oxygen; C₆-C₂₄ hydrocarbon, i.e., amolecular fragment having 6-24 carbon atoms and sufficient hydrogenatoms to complete the valencies of the carbon atoms; C₈-C₂₂ fragment;C₈-C₂₂ hydrocarbon; C₁₀-C₂₀ fragment; C₁₀-C₂₀ hydrocarbon; C₁₂-C₁₈fragment; and C₁₂-C₁₈ hydrocarbon. In various embodiments, R has atleast 6, or at least 8, or at least 10, or at least 12, or at least 14,or at least 16 carbon atoms. In various embodiments, R has no more than30, or no more than 26, or no more than 24, or not more than 22, or nomore than 20, or no more than 18 carbon atoms. The term R may representan alkyl group, where the term alkyl refers to linear, branched orcyclic saturated hydrocarbon groups, generally having any of the numberof carbon atom ranges specified above (e.g., C6-C24 refers to an alkylgroup having 6 to 24 carbon atoms). Examples of alkyl groups include3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, caprylic, capric,lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, andbehenic.

The following several paragraphs provide exemplary specific surfactantcategories and examples of specific amphoteric surfactants that may beincorporated into the fluid compositions of the present disclosure. Itshould be noted that the categories are not mutually exclusive in that aspecific amphoteric surfactant may fall into more than one category,i.e., two categories may overlap in terms of the surfactants that areencompassed within a category. There is a diverse nomenclature used inthe surfactant art to categorize and recognize classes of amphotericsurfactants specifically, and surfactants in general, where thatnomenclature often does not provide for mutually exclusive categories ofsurfactants. Nevertheless, the following provides for amphotericsurfactants useful in the present disclosure. For convenience, thesurfactant may be identified by reference only to its charged portion.For instance, the amphoteric surfactant may be referred to as a betaine,or a betaine surfactant in order to indicate that the amphotericsurfactant contains a betaine group. As another example, when theamphoteric surfactant comprises a hydroxysultaine group, such asurfactant may be referred to either as a hydroxysultaine surfactant, orwhen the context permits, even more simply as a hydroxysultaine.Alternatively, it may be said that the amphoteric surfactant comprises aspecifically identified charged group such as a betaine or betainegroup, a hydroxysultaine group, an amine oxide group, etc.

In some of the following chemical structures the term “L” is used torefer to a linking group. A linking group is a short chain of atoms thatlinks together two noted functional groups present in the amphotericsurfactant. In one embodiment, L is methylene, i.e., —CH₂—. In oneembodiment, L is ethylene, i.e., —CH₂CH₂—. In one embodiment, L ispropylene, i.e., —CH₂CH₂CH₂—. The linking group may include asubstituent on an alkylene chain, where the substituent may be, e.g.,halogen, hydroxyl or short-chain (about C₁-C₄) alkyl. In one embodiment,L is hydroxyl substituted propylene, e.g., —CH₂CH(OH)CH₂—. In anotherembodiment, L is methyl substituted methylene, e.g., —CH(CH₃)—. In oneembodiment, L is methylene, ethylene or propylene, each optionallysubstituted with hydroxyl. In one embodiment, L is dimethylether, i.e.,—CH₂-O-CH₂—. In one embodiment, L is a chain of 1-5 atoms selected fromcarbon and oxygen, where the chain is optionally substituted withhydroxyl or halide.

Any of the following terms may be used to specifically recite an“amphoteric surfactant” to thereby provide a selection of amphotericsurfactants that are useful in an embodiment of the present disclosure:alkyl amidopropyl betaine, alkyl amine oxide, alkyl amphoacetates, alkylbetaine, alkyl carboxyglycinate, alkyl glycinate, alkyl sulphobetaine,sultaine, alkyl amphopropionates, alkylamphoglycinates, alkylamidopropyl hydroxysultaines, acyl taurate and acyl glutamate. Each ofthese terms is known in the art, and many of these terms are describedbelow.

In one embodiment, the amphoteric surfactant is a betaine surfactant,which means that the surfactant includes a betaine group. The betainesurfactant may be an alkyl amido propyl betaine which may be representedby the chemical structure CH₃—(CH₂)_(n)—CONH—CH₂CH₂CH₂—N(CH₃)₂—CH₂—COOXwhen the alkyl group is a linear alkyl group. More generally, an amidopropyl betaine may be represented by the chemical structureR—CONH—CH₂CH₂CH₂—N(CH₃)₂—CH₂—COOX. These are both examples of alkylamido betaines.

In one embodiment, the amphoteric surfactant is an alkyl amidosulfobetaine which may be represented by the chemical structureR—CONH-L-N(CH₃)₂—(CH₂)_(m)—SO₂OX wherein L is propylene. A subset ofthis class is the alkylbenzene dimethyl ammonium propanesulfonatesobtained by quaternization of the alkylbenzene dimethyl amine withpropanesulfone. Again, the propylene linking group L may be substituted,e.g., with a hydroxyl group (which provides for2-hydroxy-1-propanesulfonate derivatives) to provide another amphotericsurfactant suitable for use in the present compositions.

In one embodiment, the amphoteric surfactant is an alkyl amino acidamphoteric surfactant which may be represented by the chemical structureR—NH-L-COOX, where R and L are defined above. For example, R may bederived from coconut oil, L may be ethylene and X may be sodium ion.

In one embodiment, the amphoteric surfactant is an alkyl betaineamphoteric surfactant which may be represented by the chemical structureR—N(CH₃)₂-L-COOX where R is an alkyl group and L is a linking group. Aswith other amphoteric surfactants disclosed herein, the R group may be afatty group rather than being limited to an alkyl group, however in oneembodiment the R represents an alkyl group. As mentioned previously, thelinking group may be, and in one embodiment is a methylene group.However alkyl betaines also include the α-(N,N,N-trialkyl ammonium)alkanoates, having the structure R¹—N(R²)(R³)—C(R⁴)H—COOX where L is analkyl substituted methylene group. Various alternative and sometimesmore specific names are used to name alkyl betaines, for example,N-alkyl-N,N-dimethylglycine; N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine; alkyl-dimethyl ammonium acetate or alkyl-dimethylammonium ethanoate. The Cosmetic, Toiletry and Fragrance Association,Inc. (CTFA) uses the name alkyl-betaine for these products.

In one embodiment, the amphoteric surfactant is an alkyl imidazolinederived amphoteric surfactant which may be represented by the chemicalstructure R—CONH-L-N(CH₂CH₂OH)CH₂COONa. In another embodiment, the alkylimidazoline derived amphoteric surfactant is a diacid which may berepresented by the chemical structure R—CON(CH₂CH₂OH)-L-N(CH₂COONa)2. Ineither of these embodiments, the linker L is optionally ethylene.

In one embodiment, the amphoteric surfactant is an alkyl imino diacidamphoteric surfactant which may be represented by the chemical structureR—N(CH₂CH₂COONa)₂. In alternative embodiments, the alkyl imino diacidamphoteric surfactant is represented by the chemical structureR—N(CH₂CH₂CH₂COONa)₂ or R—N(CH₂COONa)₂.

In one embodiment, the amphoteric surfactant is an alkyl sulfobetaineamphoteric surfactant. The chemical structure of an alkyl sulfobetainemay be represented as R—N(CH₃)₂-L-SO₂OX (also sometimes represented as-L-SO₃X) where R is alkyl and L is methylene. The following areexemplary of specific alkylsulfobetaines that may be used in thepractice of the present invention: caprylyl sulfobetaine, hexadecylsulfobetaine, lauryl sulfobetaine, myristyl sulfobetaine, n-octylsulfobetaine, palmityl sulfobetaine, tetradecyl sulfobetaine,

In one embodiment, the amphoteric surfactant is an alkyl sultaine, whichis a term favored by CTFA. Alkyl sultaine are sulfobetaine amphotericsurfactants that include the propanesulfonate group, i.e., L-SO₃Xwherein L is propylene. An alkyl sultaines has the chemical structureR—N(CH₃)₂—CH₂CH₂CH₂-SO₂OX.

In one embodiment, the amphoteric surfactants is an amido propyl betainewhich may be represented by the chemical structureR(C═O)—NH—(CH₂)₃—N(CH₃)₂—CH₂COOX. This class of amidopropyl betaine mayalso be referred to as an alkyl amido propyl betaine since R may bealkyl group. An alkylamidopropyl betaine surfactant is typicallysynthesized by reaction of a fatty acid, for example the fatty acid fromnatural oils such as coconut oil, and 3,3-dimethylaminopropylamine toprovide an amidopropyl dimethylamine intermediate, which in turn isreacted with sodium monochloroacetic acid to provide the correspondingbetaine. A betaine surfactant is commonly named after the source of thefatty acid used in its preparation, e.g., coconut oil provides forcocamidopropyl betaine, and isostearic acid provides forisostearmidopropylbetaine. Many alkylamidopropyl betaine surfactantssuitable for use in the present invention are commercially available insolid and solution form, and may be purchased from various suppliers.

The following are specific exemplary amidopropyl betaines that may beused in the practice of the present invention: almondamidopropylbetaine, apricotamidopropyl betaine, avocadamidopropyl betaine,babassuamidopropyl betaine, behenamidopropyl betaine, canolamidopropylbetaine, capryl/capramidopropyl betaine (formed from a mixture ofcaprylic acid and capric acid), coco/oleamidopropyl betaine,coco/sunfloweramidopropyl betaine (formed from a blend of coconut andsunflower seed oils), cupuassuamidopropyl betaine (formed from the pulpof the cupuassu tree), isostearamidopropyl betaine, lauramidopropylbetaine, meadowfoamamidopropyl betaine (formed from meadowfoam seedoil), milkamidopropyl betaine, minkamidopropyl betaine (formed from minkoil), myristamidopropyl betaine, oatamidopropyl betaine (formed fromAvena Sativa (oal) kernel oil), oleamidopropyl betaine, olivamidopropylbetaine, palmamidopropyl betaine (formed from palm oil),palmitamidopropyl betaine, palm kernelamidopropyl betaine (formed frompalm kernel oil), ricinoleamidopropyl betaine, sesamidopropyl betaine,shea butteramidopropyl betaine (formed from Butyrospermum Parkii (sheabutter)), soyamidopropyl betaine, stearamidopropyl betaine,tallowamidopropyl betaine, undecylenamidopropyl betaine, and wheatgermamidopropyl betaine (formed from the oil in wheat germ).

In one embodiment, the amphoteric surfactant is an amine oxideamphoteric surfactant which may be represented by the chemical structureR—N(CH₃)₂—O— where R is a lipophilic group. An exemplary R group is alipophilic alkyl group, where amine oxide surfactants having an alkylgroup for R are commonly known as alkyl amino oxides. Exemplary alkylgroups are caprylic, capric, lauric, myristic, palmitic, stearic, oleic,linoleic, linolenic, and behenic. Exemplary amine oxide amphotericsurfactants include cocamidopropylamine oxide and lauryldimethylamineoxide (also known as dodecyldimethylamine oxide,N,N-Dimethyldodecylamine N-oxide, and DDAO), soyamidopropylamine oxideand myristamine oxide. The nitrogen atom of the amine group may bebonded to two methyl groups as shown above, however as an alternative,the nitrogen atom may be bonded to two hydroxyethyl group to provide thestructure R—N(CH₂CH₂OH)₂—O—.

In one embodiment, the amphoteric surfactant is an amino acid amphotericsurfactant. This type of amphoteric surfactant displays a zwitterionicstructure within a certain pH range, which depends on the structure ofthe surfactant. A common example of this type of amphoteric surfactantis the amino acids of the structure R—NH—CH₂CH₂—COOH where R is a fattygroup. These are sometimes referred to as fatty amino acids, or moreprecisely as fatty aminopropionates when in the correspondingcarboxylate form. A variation on this structure has two carboxylic acidgroups, i.e., has the structure R—N(CH₂CH₂COOH)₂, which are named asfatty iminodipropionates when in the corresponding carboxylate form. Anyof these classes of amphoteric surfactants may be used in thecompositions of the present disclosure.

In one embodiment, the amphoteric surfactant is an amphoacetateamphoteric surfactant which includes the chemical structure —CH₂-CO₂X inaddition to a fatty group and a chemical group that will become positivecharged under suitable pH. These surfactants are sometimes referred toas amphoglycinates. In one embodiment, the amphoacetate amphotericsurfactant may be represented by the chemical structureR(CO)NH—CH₂CH₂—N(CH₂CH₂OH)(CH₂CO₂X) wherein R may be an alkyl group orR(CO) may be a fatty acyl group derived from a fatty acid such as foundin coconut oil to provide, e.g., cocoamphoacetate. Such amphoacetatesurfactants may be prepared by reacting a compound of formulaR(CO)NH—CH₂CH₂—NHCH₂CH₂OH with formaldehyde and a cyanide as disclosedin U.S. Pat. No. 6,232,496. Under appropriate conditions, thisamphoacetate may interconvert to the corresponding amphoacetateamphoteric surfactant comprising an imidazolium group which provides apositively charged chemical group, such as lauroamphoacetate (sodiumsalt).

The amphoacetate amphoteric surfactant may comprise two, rather thanone, acetate group, to provide an amphoteric surfactant having thechemical structure R(CO)NH—CH₂CH₂—N(CH₂CH₂OCH₂CO₂X)(CH₂CO₂X). Exemplaryamphoacetate amphoteric surfactants include disodium cocoamphodiacetate,sodium cocoamphoacetate, disodium lauroamphoacetate, and sodiumlauroamphoacetate.

In one embodiment, the amphoteric surfactant is an amphopropionateamphoteric surfactant which includes the chemical structure —CH₂CH₂—CO₂Xin addition to a fatty group and a chemical group that will becomepositive charged under suitable pH. Such amphoteric surfactants may beprepared from acrylic acid as described in U.S. Pat. No. 6,030,938.Exemplary amphopropionate amphoteric surfactants are the sodium salts ofcapryloamphopropionate, lauriminodipropionate, isostearylamphopropionate and cocoamphopropionate. The amphopropionate amphotericsurfactant may comprise two, rather than one, propionate group, toprovide an amphoteric surfactant having the chemical structureR(CO)NH—CH₂CH₂—N(CH₂CH₂OCH₂CH₂CO₂X) (CH₂CH₂CO₂X). This subclass ofamphopropionate amphoteric surfactants is known as amphodipropionateamphoteric surfactants, where exemplary amphodipropionate amphotericsurfactants are the disodium salt of cocoamphodipropionate (also knownas N-(2-coconut oilamidoethyl)-N-(2-(2-carboxyethyl)oxyethyl)-beta-aminopropionic acid,disodium salt) and capryloamphodipropionate.

In one embodiment, the amphoteric surfactant is a betaine surfactant.Betaine refers to surfactant molecules incorporating both a positivelycharged (cationic) functional group such as a phosphonium or quaternaryammonium group which bears no hydrogen atom, and a negatively charged(anionic) functional group such as a carboxylate group or an oxyanion.In a betaine, the cationic and anionic groups are not adjacent to oneanother. The betaine surfactants as referred to herein will meet theforegoing definition, and will in addition have a lipophilic moiety. Inone embodiment, the cation is a quaternary amine. In one embodiment, theanion is carboxylate. In another embodiment the anion is oxyanion. Inanother embodiment the anion is sulfate. In another embodiment, theanion is sulfonate. In another embodiment, the anion is phosphate. Manycommercially available betaines have a dialkyl substituteddimethylammonium group. Despite the prevalence of this group incommercial amphoteric surfactants, the amphoteric surfactants useful inthe present disclosure do not necessarily (although they may) have adimethylammonium group. More generally, they have a dialkylammoniumgroup, so as to provide, e.g., a trialkylammonium alkanoate of thechemical structure R¹—N(R²)(R³)—CH₂COOX. In other words, R² and R³ arenot necessarily methyl. Some exemplary betaines are alkyldimethylbetaines of the chemical structure R—N(CH₃)₂—CH₂—COOH, and alkylamidopropyldimethylbetaines of the structureR—CONH—CH₂CH₂CH₂—N(CH₃)₂—CH₂—COOH.

In one embodiment, the amphoteric surfactant is a hydroxysultaine havingthe chemical structure R—N(CH₃)₂—CH₂CH(OH)—SO₃X where R is a fattygroup, e.g., a long chain alkyl group. A hydroxysultaine is often namedafter the source of the R group, so that, for example, a hydroxysultainederived from coconut oil may be named cocamidopropyl hydroxysultaine(however it is also known as coco hydroxysulfaine, and CAHS). Otherexemplary hydroxysultaine amphoteric surfactants include lauramidopropylhydroxysultaine, oleamidopropyl hydroxysultaine, tallowamidopropylhydroxysultaine, erucamidopropyl hydroxysultaine, and laurylhydroxysultaine.

In one embodiment, the amphoteric surfactant is an imidazolinederivative amphoteric surfactant, sometimes referred to as animidazolinium derivative. Representing the chemical structure of animidazoline derivative amphoteric surfactant is complicated by the factthat imidazolines characteristically hydrolyze when exposed to water.Fatty imidazolines hydrolyze slowly on exposure to moist air, giving analkyl amidoamine. Accordingly, the alkyl amidoamine amphotericsurfactants already described elsewhere herein, are examples ofimidazolinium derivative amphoteric surfactants. In general,imidazolinium derivative amphoteric surfactants, sometimes referred toas imidazoline amphoterics, are well known in the art as a class ofsurfactant. In one embodiment, the amphoteric surfactant is animidazoline derivative, optionally a fatty alkyl imidazoline. This typeof amphoteric surfactant form cations in acidic solutions, anions inalkaline solutions, and ‘zwitterions’ in mid-pH range solutions. Themid-pH range, also referred to as the isoelectric range, within whichthe imidazoline surfactant has a neutral charge, is compound specificand depends on the precise structure of the compound, which will affectthe alkalinity of the nitrogen atom and the acidity of the carboxylicgroup. Exemplary suitable imidazoline type amphoteric surfactantsinclude, without limitation, 2-cocoyl-2-imidazoliniumhydroxide-1-carboxyethyloxy disodium.

The imidazolinium derivative amphoteric surfactant may be prepared byreaction of sodium chloroacetate and the corresponding2-alkyl-1-(2-hydroxyethyol-)-2-imidazoline. This reaction product iscommonly assigned to have the following chemical structure:

wherein R is a hydrophobic group. The reactions that produce thesecyclic imidazolinium derivatives can be readily extended to provide thecorresponding open chain molecules having the following structures:RCO—NH—CH₂CH₂—N(CH₂CH₂OH)CH₂COO— (with one equivalent of sodiumchloroacetate) and RCO—NH—CH₂CH₂—N(CH₂CH₂OH)(CH₂COO—)₂ (with twoequivalents of sodium chloroacetate). Such open chain structures areoften called imidazoline derivatives, or alkyl (when R is an alkylgroup) amido amino acids (when a single equivalent of sodiumchloroacetate has been employed in its preparation).

Commercially available amphoteric imidazolinium may be one or more ofthe foregoing structures, which are suitable for use in the presentdisclosure. A little care should be taken in selecting the imidazoliniumderivative because the same term is somewhat confusingly used to referto cationic (as opposed to amphoteric) surfactants that incorporate orare prepared from imidazolines, e.g., the cationic surfactants havingthe following structure:

Accordingly, those skilled in the art will sometimes refer specificallyto amphoteric imidazolinium surfactants to distinguish from so-calledimidazolinium surfactants that are cationic.

Examples of suitable amphoteric imidazolinium derivatives having Rgroups selected from C6-C22 alkyl, e.g., caprylic, capric, lauric,myristic, palmitic, stearic, oleic, linoleic, linolenic, and behenic.

In one embodiment, the amphoteric surfactant is a phosphinatebetaineamphoteric surfactant. Phosphinatebetaines are similar to alkybetainesand sulfobetaines where the carboxy or sulfonic group has been replacedby a phosphine group. A phosphinatebetaine may be represented by thechemical structure R—N(CH₃)₂-L-P(═O)(R)OX. L may be, for example,propylene.

In one embodiment, the amphoteric surfactant is a phosphonatebetaineamphoteric surfactant. Phosphonatebetaines are similar to alkybetainesand sulfobetaines where the carboxy or sulfonic group has been replacedby a phosphonate group. A phosphonatebeaine may be represented by thechemical structure R—N(CH₃)₂-L-P(═O)(OR)OX. L may be, for example,propylene.

In one embodiment, the amphoteric surfactant is a pyridinium alkanoateamphoteric surfactant, which may be represented by the chemicalstructure

where R is a fatty group, e.g., a medium or long chain alkyl. Thepyridinium alkanoate illustrated in the carboxylic acid form, however atsuitable pH the carboxylic acid (—COOH) group will convert to thecarboxylate (COOX) group.

In one embodiment, the amphoteric surfactant is a sulfate ion-containingamphoteric surfactant. The sulfate ion group may be readily added tofatty unsaturated amines, such as oleylamine (1-amino-9,10-octadecene)to provide the corresponding sulfate ion-containing amphotericsurfactant with the name 9-(10)-hydroxyoctadecylamine.

In one embodiment, the amphoteric surfactant is a sulfatobetaine, alsoknown as an alkyldimethylammonium alkyl sulfate, which may berepresented by the chemical structure R—N(CH₃)₂-L-OSO₃X. Sulfatobetainesare examples of sulfate ion-containing amphoteric surfactants that alsocontain the betaine group.

In one embodiment, the amphoteric surfactant is a sulfobetaineamphoteric surfactant. The chemical structure of the basic compound maybe represented as R—N(CH₃)₂-L-SO₂OX (also sometimes represented as-L-SO₃X). As commercially available, many sulfobetaines have L aspropylene, and such amphoteric surfactants may be used in an embodimentof the present disclosure. Sulfobetaines are an example of sulfonicacid-containing amphoteric surfactants which also include a betainegroup. This class of betaine amphoteric surfactant includes ammoniumalkane sulfonates and 2-(N-alkyl-N,N-dimethylammonium) ethanesulfonates. Sulfobetaines also include trialkyl ammonium compoundssimilar to alkylbetaines but having the carboxyl group replaced by analkylsulfonate group. When R is a lipophilic alkyl group, this class ofsulfobetaine may be referred to as an alkylsulfobetaine. Thealkylsulfobetaine surfactants are commonly named after the long chainalkyl group present in their structure. For example, when R has 12carbons atoms in a straight chain, i.e., is lauryl, the correspondingsulfobetaine is known as lauryl sulfobetaine.

There are a great many sulfobetaine surfactants which are a variation onthe classic structure shown above. For example, the propylene ((CH₂)₃)group designated by “L” may be substituted with various functionalgroups, e.g., halogen, hydroxyl, and methoxy. The R group need not be astraight chain alkyl group, but may be a branched or even alicyclic oraromatic hydrocarbon. Indeed, the R group need not even be ahydrocarbon. Primarily, the R group needs to be lipophilic, and a greatmany chemical structures provide that property. Examples of sulfobetainesurfactants suitable for use in the present invention but which do notfall within the scope of the classic structure shown above areN-(3-cocoamidopropyl)-N,N-dimethyl-N-(2-hydroxy-3-sulfopropyl)ammoniumbetaine, and 3-[(3-chloroamidopropyl)dimethylammonium]-1-propanesulfonate.

In one embodiment, the amphoteric surfactant is a sulfonicacid-containing amphoteric surfactant. For example, the amphotericsurfactant may be an N-alkyl taurine of the chemical formulaRNH—CH₂CH₂—SO₃H where R is an alkyl group. In a related embodiment, R isa fatty group. Another sulfonic acid-containing amphoteric surfactantmay be prepared by sulfonation of the linear amidoamine precursor to1-hydroxyethyl 2-alkyl imidazoline, so as to provideR—CONH—CH₂CH₂—N(CH₂CH₂OH)CH₂CH₂SO₃H where R may be a fatty group, e.g.,an alkyl group.

Specific examples of amphoteric surfactants and classes thereof that maybe used in the present compositions include, without limitation,cocoamidopropylamine oxide, cocamidopropyl betaine, cocamidopropylhydroxysultaine, cocodimethyl sulphopropyl betaine, disodiumcocoamphodipropionate, lauryl amine oxide, lauryl amido propyl betaine;lauryl betaine, lauryl hydroxyl sulfobetaine, myristamine oxide, sodiumcocoamphoacetate, and stearyl betaine. As mentioned previously, theseterms do not necessarily define mutually exclusive groups ofsurfactants, i.e., a specific amphoteric surfactant may fall within thescope of two or more sets of amphoteric surfactants each defined one ofthe selected terms.

Anionic Surfactant

In one embodiment, the fluid compositions of the present disclosureinclude at least one, and optionally include more than one, anionicsurfactant. Suitable exemplary anionic surfactants include, withoutlimitation, alkyl sulfates, alkylether sulfates, alkylsulfonates,alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates,N-alkoylsarcosinates, acyl taurates, acyl isethionates, alkylphosphates, alkyl ether phosphates, alkyl ether carboxylates,.alpha.-olefinsulfonates, and the alkali metal and alkaline earth metalsalts and ammonium and triethanolamine salts thereof. Such alkyl ethersulfates, alkyl ether phosphates and alkyl ether carboxylates can havebetween 1 and 10 ethylene oxide or propylene oxide units, and in someembodiments, 1 to 3 ethylene oxide units, per molecule. For convenience,an anionic surfactant may be referred to by reference to the anionicgroup that forms the charged portion of the surfactant. For example, ananionic surfactant that comprises a sulfonate group may be referred toas a sulfonate surfactant, or even more simply when the context permits,as a sulfonate. As a further example, an anionic surfactant thatcomprises a sulfate group may be referred to as a sulfate surfactant, orwhen the context permits, even more simply as a sulfate.

In one embodiment, the anionic surfactant is a carboxylic acid orcarboxylate, having the anionic group —C(O)—O— in addition to a fattygroup. The fatty group, designated R herein, may be an alkyl group, inwhich case the carboxylate may be referred to as an alkyl carboxylate.Exemplary alkyl carboxylates are the sodium or potassium or ammoniumsalts of fatty acids such as stearic acid and oleic acid. Potassiumoleate is an exemplary alkyl carboxylate. The fatty group mayalternatively be a polyalkylene oxide group which is not water soluble.Some carboxylate anionic surfactants are prepared from an alkyl alcohol,such as octanol, which is then reacted with ethylene oxide to providethe polyoxyethyelene extended octanol known as polyoxyethylene (8) octylether carboxylic acid, when the average number of ethylene oxide unitsper molecule is 8.

In one embodiment, the anionic surfactant is a diphenyl oxide. Adiphenyloxide may also be viewed as a subclass of sulfonate anionicsurfactants, since the aromatic rings of the diphenyl precursor issulfonated in order to provide the diphenyl oxide anionic surfactant.The diphenol precursor is typically a diphenylether, i.e., Ar—O—Ar,where one or both of the aromatic rings (Ar) may be substituted with analkyl group. The diphenyl oxide anionic surfactant may be represented bythe chemical formula XSO₃—Ar(R)—O—Ar(R)—SO₃X where R is hydrogen oralkyl at each position of the aromatic ring that is not sulfonated orbonded to the ether oxygen. Exemplary diphenyl oxide anionic surfactantsinclude disulfonated diphenyl oxide with alkyl substitution such asdisulfonated diphenyl oxide with linear decyl substitution, disulfonateddiphenyl oxide with linear dodecyl substitution, disulfonated diphenyloxide with branched decyl substitution, any of which may be neutralizedwith sodium, potassium or ammonium.

In one embodiment, the anionic surfactant is a phosphate ester, whichmay be a monophosphate ester of the chemical structure R—O—P(O)(OH)₂,i.e., or a phosphate diester of the chemical structure R—O—P(O)(OH)—O—Rwhere the two Rs in the diester may be the same or different. The Rgroup is a fatty group, i.e., a non water soluble group. The R group maybe an alkyl group, and phosphate esters having R═alkyl are typicallymade from the corresponding alkyl alcohol. In one embodiment, the Rgroup is a polyalkylene oxide group so as to provide a polyetherphosphate ester of the formula R—(OCH₂CH₂)_(n)—O—P(O)(OH)₂. A commonnaming convention for polyether phosphate esters provides the number ofpolyoxyethylene groups in the surfactant, e.g., polyoxyethylene (10).The R group in the polyether phosphate may be an alkyl group (when thepolyether phosphate is derived from an alkyl alcohol), an aryl group(when the polyether phosphate is derived from an aromatic alcohol, e.g.,phenol), or an alkyl aryl group, e.g., alkyl-substituted phenol such asnonyl-phenol. Exemplary phosphate esters include polyoxyethylene (10)nonylphenol phosphate, polyoxyethylene (4) phenol phosphate, and C₈H₁₇phosphate. Commercial preparations of phosphate esters often provide amixture of phosphate monoester and phosphate diester, which may be usedin the compositions of the present disclosure.

In one embodiment, the anionic surfactant is a sarcosinate, i.e., acompound having the chemical structure R—C(O)—N(CH₃)—CH₂—CO₂X where R isa fatty group. The sarcosinate surfactants include an N-acyl group,where the fatty acid from which the acyl is derived is typically used toname the sarcosinate. Exemplary sarcosinates include sodium lauroylsarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate,and the ammonium ion equivalents.

In one embodiment, the anionic surfactant is a sulfate, i.e., a compoundhaving the anionic —O—SO₃X group in addition to a fatty group. The fattygroup may be a long chain alkyl group, where an alkyl group in asurfactant may be branched or straight chain. The fatty group need notbe an alkyl group, however alkyl groups are commonly available from manyplant and animal oils, and so are a ready source of fatty groups forsurfactants. Exemplary sulfate anionic surfactants include sodiumlaureth sulfate, sodium dodecyl sulfate, sodium decyl sulfate, sodiumoctyl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, sodiumrrideceth sulfate, C₁₂-C₁₄-tert-alkyl-ethoxylated sodium sulfate, andpoly(oxy-1,2-ethanediyl), α-sulfo-ω-(nonylphenoxy) ammonium salt.

In one embodiment, the anionic surfactant is a sulfoacetate, i.e., acompound having the anionic —CH₂—SO₃X group in addition to a fattygroup. A common fatty group has the structure R—O—C(O)—, where R is analkyl group, e.g., C₈-C₁₈ straight chain alkyl. Exemplary sulfoacetateanionic surfactants are sodium lauryl sulfoacetate and the ammonium saltof cetyl sulfoacetate. Sulfoacetates may be prepared as described in,e.g., U.S. Pat. No. 5,616,782.

In one embodiment, the anionic surfactant is a sulfonate, i.e., acompound having the anionic —SO₃X group in addition to a fatty group.The fatty group may be, for example, a long chain alkyl group. Thesulfonate may be regarded as having the chemical structure R—SO₃X. Inone embodiment, the R group is derived from a fatty acid, and is astraight long chain alky group such as stearyl and oleyl. Long chainolefins are often used as precursors to sulfonates, since the doublebond may be treated to convert it to a sulfonate group. Such sulfontesare often named by the precursor which is used to form the sulfonate,such as C₁₄-C₁₆ olefin sulfonate, where C₁₄-C₁₆ denotes that a mixtureof olefins having 14 and 16 carbons was sulfonates to provide theanionic surfactant. In one embodiment, the R group is an alkylbenzenegroup, for example, a dodecylbenzene group. The alkyl group, e.g., thedodecyl group, may be a linear alkyl group or a branched alkyl group.Exemplary sulfonate anionic surfactants are linear dodecylbenzenesulonate and branched dodecylbenzene sulfonate. As always, the anionicgroup may be neutralized with any suitable cation, e.g., sodium,potassium, ammonium, etc.

In one embodiment, the anionic surfactant is a sulfosuccinate, i.e., acompound having the chemical structure based on sulfonated succinicacid, i.e., Fatty Group-O—C(O)—CH₂—CH(sulfate)-C(O)—O—R (which may be afatty group or hydrogen). Sulfosuccinates are generally sodium salts ofalkyl esters of sulfosuccinic acid that are a result of condensation ofmaleic anhydride with a fatty alcohol, followed by sulfonation withsodium bisulfite (NaHSO₃). As shown by the foregoing chemical structure,a sulfosuccinate will have at least one fatty group, and may have twofatty groups. However, when the sulfosuccinate has one fatty group, itmay also have an anionic carboxylate group rather than a second fattygroup. Exemplary sulfosuccinate anionic surfactants include sodiumdioctyl sulfosuccinate (having two fatty groups) and disodium laurethsulfosuccinate (which has one fatty group, one sulfate group and onecarboxylate group, and is also known as DLS).

Additional specific examples of anionic surfactants include, withoutlimitation, ammonium lauryl sulfosuccinate, sodium lauryl sulfate,sodium lauryl ether sulfate, ammonium lauryl ether sulfate,triethanolamine dodecylbenzenesulfonate, sodium lauryl sarcosinate,ammonium lauryl sulfate, sodium oleyl succinate, sodium dodecyl sulfate,and sodium dodecylbenzene sulfonate.

In one embodiment, the fluid concentrations and compositions of thepresent disclosure contain a third surfactant selected from amphotericand anionic surfactants. The third surfactant is non-identical to, i.e.,is not the same as, either of the first (the amphoteric) or the second(the anionic) surfactants. Any of the amphoteric and anionic surfactantsdisclosed previously are optionally used as the third surfactant in thepresent formulations, so long as it (the third surfactant) is not thesame as the first or second surfactant. In one embodiment, the thirdsurfactant is of a different class from the first or second surfactant,i.e., the third surfactant has a different functional group from thefunctional groups that provide the charged functionality present in thefirst and second amphoteric or anionic surfactant. For example, if thesecond surfactant is a sulfate anionic surfactant, then the thirdsurfactant is not a sulfate, but is instead, e.g., a sulfonate anionicsurfactant.

Amphoteric and/or anionic surfactants suitable for use in the presentinvention may be obtained from one or more of the following exemplarymanufacturers and/or suppliers: Aceto Corp. (Allendale, N.J.); AirProducts (Allentown, Pa.); Akzo Nobel Chemicals Co. (Chicago, Ill.);Alzo International (Sayreville, N.J.); BASF Corp. (Florham Park, N.J.);Clariant Corp. (Frankfurt, Germany); Croda, Inc. (Edison, N.J.); DowChemical (Midland Mich.); E. I. du Pont de Nemours & Co., Inc.(Wilmington, Del.); Harcros Chemicals, Inc. (Kansas City, Kans.);Huntsman Corp. (St. Lake City, Utah); Kaiser Industries Ltd.(Bahadurgarh, Haryana, India), Kao Chemicals. (Tokyo, Japan); Lonza,Inc. (Basel, Switzerland); NOF Corporation (Tokyo, Japan); PilotChemicals (Cincinnati, Ohio); Procter & Gamble (Cincinnati, Ohio);Solvay-Rhodia (Courbevoie, France); Stepan Co. (Northfield, Ill.); andUnilever PLC (London, England).

Optional Components

The following ingredients are optionally present in the compositions ofthe present disclosure, however the present disclosure also providesthat each of the following ingredients may be specifically excluded frombeing present in the composition of the present disclosure.

The compositions of the present disclosure may include an anti-rustagent, which may also be referred to herein as an anti-corrosion agent.An exemplary anti-rust agent is sodium nitrite. Other exemplaryanti-rust agents are sodium benzoate, organic boron compounds, amines,aminophosphate compounds, zinc dialkyldithiophosphate, and tall oilfatty acids. The anti-rust agent may be present in the composition at anamount of less than 10 wt % of the composition directly used as amaterial fabrication fluid, e.g., as a metal cutting fluid. In optionalembodiments, that amount is less than 9 wt %, or less than 8 wt %, orless than 7 wt %, or less than 6 wt %, or less than 5 wt %, or less than4 wt %, or less than 3 wt %, or less than 2 wt %, or less than 1 wt %,or less than 0.5 wt %, or less than 0.1 wt %. The amount may also beexpressed in terms of a minimum amount, such as at least 500 ppm, or atleast 1000 ppm, or at least 1500 ppm, or at least 2000 ppm, or at least2500 ppm, 0.5 wt %, or at least 1 wt %, or at least 1.5 wt %, or atleast 2 wt %, or at least 2.5 wt %, or at least 3 wt %, or at least 3.5wt %, or at least 4 wt %, or at least 4.5 wt %, or at least 5 wt %.Anti-rust agents are well known commercial materials.

The compositions of the present disclosure may include a colorant, suchas a dye or pigment. The coloring agent should be used in a smallamount, just enough to impart color visible to the eye, when thecomposition is being applied to material, e.g., metal, to be cut orotherwise shaped. Colorants are well known commercial materials.

The compositions of the present disclosure may include a de-foamingagent which may also be referred to as an anti-form agent. A suitablede-foaming agent is a silicone polymer. Silicone defoaming agents arewell known commercial materials. Dow Corning (Michigan, USA) sells suchde-foaming agents. Another suitable de-foaming agent istributylphosphate.

The compositions of the present disclosure may include a thickeningagent. As used herein, upon addition to, or inclusion in, an aqueousfluid composition or concentrate thereof, the thickening agent increasesthe viscosity of the composition. The inclusion of a thickening agentprovides for, among other things, an improved adhesion of thecomposition to a surface. This is particularly advantageous when thesurface is not horizontal and so the material fabrication compositionwill tend to fall down the surface under the force of gravity absent thepresent of a thickening agent. The thickening agent may be watersoluble. Thickening agents for aqueous compositions are well known inthe art, may be referred to as an aqueous thickening agent, and any ofsuch thickening agents may be used in the present compositions.

The amount of thickening agent to be included in the composition willdepend on the precise identity of the thickening agent and the desiredviscosity of a concentrated form of the material fabrication fluidcomposition. For a thickening agent selected from a cellulosic orpolyamide thickening agent, and to achieve a viscosity similar to thatof whole milk or orange juice, the thickening agent will typically bepresent in the composition at weight percent of 0.1 weight percent,based on the total weight of the composition, when the composition is aconcentrate having about 5-25% total solids. The viscosity of theconcentrate may be varied, primarily by the incorporation of more orless thickener. If a more viscous concentrate is desired, the additionof more thickening agent will provide for a more viscous composition.Alternatively, a more effective thickening agent may be utilized, i.e.,a thickening agent that achieves the same increase in viscosity but at alower concentration.

In one aspect, the thickening agent may be a polyhydroxy polymer, e.g.,a polysaccharide such as a cellulosic or a functionalized cellulosic.When the thickening agent is a polysaccharide, the polysaccharide mayhave at least 50, or at least 100, or at least 150, or at least 200saccharide units per polymer chain. The number average molecular weightof the polysaccharide may be at least 13,000 or at least 17,000 or atleast 21,000 or at least 25,000.

In one aspect, the thickening agent is a polyhydroxy small molecule,such as glycerol. A polyhydroxy small molecule has a molecular weight ofless than 500 g/mol and has at least three hydroxyl groups.

In one aspect, the thickening agent is a cellulosic, which includesderivatives of cellulosic resins. A suitable cellulosic ishydroxyethylcellulose (HEC). HEC is a derivative of cellulose whereinthe —CH₂OH groups are converted to —CH₂OCH₂CH₂OCH₂CH₂OH groups, and —OHgroups are converted to —OCH₂CH₂OH groups. HEC is commercially availablein many grades, which vary as to molecular weight and degree ofderivatization, which in turn lead to different solution viscosities(typically measured at 2% solids in water). Suitable HEC is Cellosize™from Dow Chemical (Midland, Mich.) and Aqualon™ from Ashland Chemical(Covington, Ky.).

Other suitable cellulosic thickening agents include methyl cellulose,ethyl cellulose, methylhydroxyethylcellulose,methylhydroxypropylcellulose, hydroxypropylcellulose, and anionic (salt)forms such as sodium carboxymethylcellulose, dihydroxypropyl ethers ofcellulose (see, e.g., U.S. Pat. No. 4,096,326),

Suitable polyhydroxy polymers other than cellulosics include corn starchor modified corn starch, potato starch or modified potato starch, andpectin or modified pectin.

The thickening agent may be a polyacrylamide. Suitable polyacrylamidethickening agents may be selected from copolymers of acrylamide andammonium acrylate; copolymers of acrylamide or methacrylamide andmethacryloyloxyethyltrimethylammonium halide, for example chloride; andcopolymers of acrylamide and 2-acrylamido-2-methylpropanesulphonic acid.These copolymers may be prepared in the presence of a crosslinkingagent, where exemplary crosslinking agents include divinylbenzene,tetraallyloxyethane, methylenebisacrylamide, diallyl ether,polyallylpolyglyceryl ethers or allylic ethers of alcohols of the sugarseries, such as erythritol, pentaerythritol, arabitol, mannitol,sorbitol and glucose. See, e.g., U.S. Pat. Nos. 2,798,053 and 2,923,692.The polyacrylamide may be ionic and neutralized with a neutralizingagent such as sodium hydroxide, potassium hydroxide, aqueous ammonia oran amine such as triethanolamine or monoethanolamine. Ionicpolyacrylamides may be prepared by copolymerizing acrylamide and sodium2-acrylamido-2-methylpropanesulphonate via a radical route usinginitiators of the azobisisobutyronitrile type and by precipitation froman alcohol such as tert-butanol. A crosslinked copolymer of acrylamideand methacryloyloxyethyltrimethyl-ammonium chloride may be obtained bycopolymerization of acrylamide and dimethylaminoethyl methacrylatequaternized with methyl chloride, followed by crosslinking with acompound containing olefinic unsaturation, such asmethylenebisacrylamide.

The thickening agent may be a polyacrylic acid. Suitable polyacrylicacid thickening agents are commercially available. For example, Lubrizol(Wickliffe, Ohio) sells their Carbopol™ synthetic thickeners that aremade from polyacrylic acid. The polyacrylic acid may be neutralized inorder to adjust its thickening behavior. For example, polyacrylic acidmay be neturalized with ammonium ions using, e.g., ammonium hydroxide.Ashland Chemical markets their Carbomer™ line of crosslinked polyacrylicacids. Again, these polymers need to be neutralized in order to provideeffective thickening behavior.

The thickening agent may be a gum or a derivative thereof. Examplesinclude locust bean gum and derivatives, guar gum and derivatives, andxanthan gum and derivatives. Exemplary gum derivatives includesulfonated gum, e.g., sulfonated guar, hydroxypropyl derivatized gum,e.g., hydroxypropyl guar, cationic derivatives, e.g., cationic guar,

The thickening agent may be a hydrophobically modified thickening agent.In one aspect, the thickening agent comprises a hydrophobic group suchas a hydrophobic alkyl chain, where suitable examples of such thickeningagents include hydrophobically modified ethylene oxide urethane (HEUR)polymer, hydrophobically modified alkali soluble emulsion (HASE)polymer, hydrophobically modified hydroxyethyl cellulose (HMHEC), andhydrophobically modified polyacrylamide (HMPA). HEUR polymers are linearreaction products of diisocyanates with polyethylene oxide end-cappedwith hydrophobic hydrocarbon groups. HASE polymers are homopolymers of(meth)acrylic acid, or copolymers of (meth)acrylic acid, (meth)acrylateesters, or maleic acid modified with hydrophobic vinyl monomers. HMHECrefers to hydroxyethyl cellulose modified with hydrophobic alkyl chains.HMPA refers to copolymers of acrylamide with acrylamide modified withhydrophobic alkyl chains (N-alkyl acrylamide).

In one aspect, the fluid composition of the present disclosure includesan inorganic salt of an organic or inorganic acid. Suitable inorganicsalts of organic acids include ammonium citrate, calcium acetate, copperacetate, copper citrate, magnesium citrate, melamine phosphate salt,nickel acetate, potassium acetate, potassium citrate, sodium acetate,sodium bitartrate, strontium acetate, urea phosphate, and zinc acetate.

The amount of inorganic component present in the composition may bevaried over a wide range. Based on the total weight of the solidspresent in the composition, the inorganic component may constitute from1% to about 15% of that weight. In various embodiments, the inorganiccomponent is at least 2%, or at least 3%, or at least 4%, or at least5%, or at least 6%, or at least 7%, or at least 8%, or at least 9%, orat least 10%, or at least 11%, or at least 12%, or at least 13%, or atleast 14%, or at least 15% of the total weight of the solid componentsof the composition. In various embodiments, the inorganic componentcontributes not more than 30%, or 25% or 20% or 15% or not more than 10%of the total weight of the solids present in the composition. Asmentioned previously, in one embodiment the inorganic component is aninorganic salt.

In one aspect, the fluid composition of the present disclosure includesa non-volatile organic solvent that is miscible with water. As usedherein, a non-volatile material or solvent that is a liquid has aboiling point of greater than water, i.e., greater than 100° C. Anexemplary organic solvent is ethylene glycol monobutyl ether, also knownas BUTYL CELLOSOLVE™.

As mentioned previously, the present disclosure provides a concentratecomposition comprising water and solids, the solids comprising a firstsurfactant selected from amphoteric surfactants, a second surfactantselected from anionic surfactants, and a third surfactant selected froman amphoteric and an anionic surfactant, the third surfactant beingdifferent from the first and second surfactants. Optionally, the thirdsurfactant, but neither of the first or second surfactants, is afluorosurfactant. The third surfactant may be a fluorinated orperfluorinated anionic fluorosurfactant while the second (anionic)surfactant of the concentrate is non-fluorinated. Alternatively, thethird surfactant may be a fluorinated or perfluorinated amphotericsurfactant while the first (amphoteric) surfactant of the concentrate isnon-fluorinated. A fluorinated surfactant will contain some C—F bondsand may contain only C—F bonds (in which case it is perfluoronated) andmay contain some C—H bonds (in which case it is ahydrofluorocarbon-containing molecule).

In addition to fluorinated versions of the amphoteric and anionicsurfactants identified herein, other exemplary fluorosurfactants thatmay be included in a concentrate or composition of the presentdisclosure include the Captstone™ fluorosurfactants and the Forafac™fluorosurfactants, both from DuPont (Wilmington, Del.). Other exemplaryfluorosurfactants are those disclosed in any of US Patent PublicationNo. US 20130112908; US 20120255651; US20110232924; US 20110091408; US20100168318; and US. Pat. Nos. 8,287,752; 8,039,677; 7,977,426; and7,989,568.

However, in another embodiment, the third surfactant is not afluorosurfactant. Fluorine-containing compounds should be used withcaution since they may have an undesirable bio-persistence profile,and/or they may break down to hazardous materials. In one embodiment,the present concentrates and compositions do not contain anyfluorocarbons, while in another embodiment the present concentrates andcompositions do not contain any halocarbons.

Formulations

The present disclosure provides material fabrication fluids, e.g., metalcutting fluids, in concentrated form as well as in diluted(ready-to-use) forms. The concentrated form may be described in terms ofthe amounts of the various components, where these amounts are relativeto the total amount of surfactant present in the concentrate.

For example, for each weight part of surfactant (e.g., for each 1g, oreach 1kg, etc. of surfactant) the concentrate may contain 1-10 weightparts of anti-rust agent. Thus, if the concentrate contains 10 grams ofsurfactant, the concentrate may also contain from 10-100 grams ofanti-rust agent. Optionally, the concentrate contains at least 1, or atleast 2, or at least 3, or at least 4, or at least 5 weight parts ofanti-rust agent (relative to 1 weight part of surfactant), and maycontain less than 10, or less than 9, or less than 8, or less than 7, orless than 6, or less than 5 weight parts of anti-rust agent. Inexemplary embodiments, the concentrate contains 1-10, or 2-8, or 3-7, or4-6 weight parts of anti-rust agent such as sodium nitrite, for each 1gram of total surfactant present in the concentrate.

For each weight part of surfactant, the concentrate may contain 0.1-0.5weight parts of thickener. Thus, if the concentrate contains 10 grams ofsurfactant, the concentrate may also contain 1-5 grams of thickener.Optionally, the concentrate contains at least 0.1 or at least 0.2, or atleast 0.3, or at least 0.4 weight parts of thickener (relative to 1weight part of surfactant(s)), and may contain less than 0.5, or lessthan 0.4, or less than 0.3 weight parts of thickener. In exemplaryembodiments, the concentrate contains 0.1-0.5, or 0.2-0.4 weight partsof thickener such as hydroxyethylcellulose, for each 1 gram of totalsurfactant present in the concentrate.

For each weight part of surfactant, the concentrate may contain0.05-0.25 weight parts of inorganic salt. Thus, if the concentratecontains 10 total grams of surfactant, the concentrate may also contain0.5-2.5 grams of inorganic salt. Optionally, the concentrate contains atleast 0.05, or at least 0.1, or at least 0.15, or at least 0.2 weightparts of inorganic salt (relative to 1 weight part of surfactant(s)present in the concentrate), and may contain less than 0.25, or lessthan 0.2, or less than 0.15, or less than 0.1 weight parts of inorganicsalt. In exemplary embodiments, the concentrate contains 0.05-0.25, or0.1-0.2 weight parts of inorganic salt such as calcium chloride.

For each weight part of surfactant, the concentrate may contain 0.01-0.1weight parts of non-volatile, water-soluble organic solvent. Thus, ifthe concentrate contains 10 total grams of organic solvent, theconcentrate may also contain 0.1-1 grams of organic solvent. Optionally,the concentrate contains at least 0.01, or at least 0.02, or at least0.03, or at least 0.04, or at least 0.05, or at least 0.06, or at least0.07 weight parts of organic solvent (relative to 1 weight part ofsurfactant(s) present in the concentrate), and may contain less than0.1, or less than 0.09, or less than 0.08, or less than 0.07, or lessthan 0.06, or less than 0.05 weight parts of organic solvent. Inexemplary embodiments, the concentrate contains 0.01-0.1, or 0.02-0.9,or 0.03-0.8 weight parts of organic solvent such as ethylene glycolbutyl ether.

For each weight part of surfactant, the concentrate may contain 0.2-1.0weight parts of defoamer. Thus, if the concentrate contains 10 totalgrams of surfactant, the concentrate may also contain 2-10 grams ofdefoamer. Optionally, the concentrate contains at least 0.2, or at least0.3, or at least 0.4, or at least 0.5 weight parts of defoamer (relativeto 1 weight part of surfactant(s) present in the concentrate), and maycontain less than 1.0, or less than 0.9, or less than 0.8, or less than0.7, or less than 0.6 weight parts of defoamer. In exemplaryembodiments, the concentrate contains 0.2-1.0, or 0.3-0.8, or 0.4-0.6weight parts of defoamer such as a silicone defoamer.

The concentrate will also contain water. The amount of water may vary,but is typically in the range of 5-50% of the weight of the concentrate.In other words, 100 grams of concentrate will include between 5 and 50grams of water. In optional embodiments, the concentrate is at least 5%,or at least 10%, or at least 15%, or at least 20%, or at least 25% byweight water, while in other optional embodiments, the concentrate isless than 50%, or less than 45%, or less than 40%, or less than 35%, orless than 30% by weight water.

The present disclosure also provides for diluted forms of theconcentrate, which are ready to use in a material fabrication process,such as a metal cutting operation. In optional embodiments, the dilutedforms of the concentrate have been diluted sufficiently that their watercontent is from 75-99%. Dilute forms of the concentrate may be dilutedby combining the concentrate with an equal volume of water (a 1×dilution), or be prepared by 2×, or 3×, or 4×, or 5×, or 6×, or 7×, or8×, or 9×, or 10×, or 11×, or 12×, or 13×, or 14×, or 15×, or 16×, or17×, or 18×, or 19×, or 20× dilution, as well as ranges providing byselecting any two of these values. For example, the diluted form may beprepared by a dilution of from 5×-15×, i.e., adding 5-15 volumes ofwater to each volume of concentrate, or by adding 5-15 weights of waterto each weight of concentrate.

In one embodiment, the present disclosure provides a compositioncomprising water and solids, the solids comprising at least onesurfactant, such as an amphoteric first surfactant, an anionic secondsurfactant, and a third surfactant selected from an amphoteric and ananionic surfactant, the third surfactant being different from the firstand second surfactants. In optional embodiments: the water comprises 75to 95 wt % of the composition; e.g., the water comprises 75 to 80 wt %of the composition or the water comprises 80 to 85 wt % of thecomposition or the water comprises 85 to 90 wt % of the composition orthe water comprises 95 to 95 wt % of the composition. In optionalembodiments: the amphoteric surfactant(s) comprises 10 to 30 wt % of thesolids or 15 to 25 wt % of the solids; e.g., the amphotericsurfactant(s) comprises 10 to 15 wt % of the solids or the amphotericsurfactant(s) comprises 15 to 20 wt % of the solids or the amphotericsurfactant(s) comprises 20 to 25 wt % of the solids or the amphotericsurfactant(s) comprises 25 to 30 wt % of the solids. In an optionalembodiment, the amphoteric surfactant(s) comprise 1 to 5 wt % of thecomposition. In optional embodiments, the anionic surfactant(s) comprise45 to 85 wt % of the solids; e.g., the anionic surfactant(s) comprise45-55 wt % of the solids or the anionic surfactant(s) comprise 55-65 wt% of the solids or the anionic surfactant(s) comprise 65-75 wt % of thesolids or the anionic surfactant(s) comprise 75-85 wt % of the solids.In an optional embodiment, the anionic surfactant(s) comprise 5 to 25 wt% of the composition.

In additional optional embodiments, the amphoteric surfactant is one ormore betaines selected from cocodimethyl sulphopropyl betaine, laurylbetaine and cocamidopropyl betaine; the anionic surfactant is one ormore surfactants selected from ammonium lauryl sulfosuccinatem, sodiumlauryl sulfate, sodium laureth sulfate, sodium lauryl ether sulfate,ammonium lauryl ether sulfate, triethanolamine dodecylbenzenesulfonate,sodium lauryl sarcosinate, ammonium lauryl sulfate, sodium oleylsuccinate, sodium dodecyl sulfate, sodium decyl sulfate, sodium octylsulfate, and sodium dodecylbenzene sulfonate; the composition furthercomprises an inorganic salt, where optionally the inorganic saltcomprises 2 to 20 wt % of the solids; the composition further comprisesa thickening agent, where optionally the thickening agent comprises 0.1to 5 wt % of the solids.

As mentioned previously, the compositions of the present disclosure mayinclude both of an amphoteric surfactant (and optionally more than oneamphoteric surfactant) and an anionic surfactant (and optionally morethan one anionic surfactant). In one aspect, the one or more amphotericsurfactant(s) contribute about an equal weight to the composition as dothe one or more anionic surfactant(s). In other aspects, and again asmeasured on a weight basis, the amphoteric surfactant(s) contribute alesser weight to the total weight of the composition than do the anionicsurfactant(s), where in various embodiments the amphoteric surfactant(s)contribute from 1 to 50%, or from 5 to 40%, or from 10 to 30% or from 15to 25% of the total weight of the anionic and amphoteric surfactants.

When the composition contains two of an amphoteric surfactant, or two ofan anionic surfactant, the two surfactants are not necessarily presentin equal weight amounts. In various embodiments, the compositioncomprises a first and a second anionic surfactant, where the firstsurfactant provides 1 to 50% of the total weight of the first and secondsurfactant. In additional embodiments, the first surfactant provides1-40%, or 1-30%, or 1-20%, or 1 to 10%, or 1 to 5% of the total weightof the first and second anionic surfactants. Likewise, in variousembodiments, the composition comprises a first and a second amphotericsurfactant, where the first amphoteric surfactant provides 1 to 50% ofthe total weight of the first and second surfactant, and in additionalembodiments, the first amphoteric surfactant provides 1-40%, or 1-30%,or 1-20%, or 1 to 10%, or 1 to 5% of the total weight of the first andsecond amphoteric surfactants.

In one embodiment, a mixture of two amphoteric surfactants are includedin a material fabrication fluid, e.g., a metal cutting fluidcomposition, of the present disclosure. For instance, mixtures of any ofthe previously mentioned amphoteric surfactants may be used. When twoamphoteric surfactants are present in a composition, those twosurfactants will be present in relative amounts, based on the weight ofeach the surfactants in the composition. For example, if the compositioncontains equal weights of the two amphoteric surfactants, then those twosurfactants are present in a weight ratio of 1:1. If the compositioncontains twice as much of a first surfactant than of a secondsurfactant, then those two surfactants are present in a weight ratio of1:2. If the second surfactant is present within a range of permissibleweights, relative to the weight of the first surfactant, and that rangeis between “equal to the weight of the first surfactant” and “twice asmuch as the weight of the first surfactant” such that those twosurfactants are present in a weight ratio of 1:(1-2).

As mentioned above, in one embodiment the present disclosure providesfor the presence of two amphoteric surfactants in a composition. Invarious embodiments, those two amphoteric surfactants may be present atany of the following relative amounts: 1:1; 1:(1-5); 1:(1-10); 1:(1-15);1:(1-20); 1:(1-25); 1:(1-30); 1:(5-10); 1:(5-15); 1:(5-20); 1:(5-25);1:(5-30); 1:(10-15); 1:(10-20); 1:(10-25); 1:(10-30); 1:(15-20);1:(15-25); 1:(15-30); 1:(20-25); and 1:(25-30).

In one embodiment, a mixture of two anionic surfactants are included ina material fabrication fluid, e.g., a metal cutting fluid composition,of the present disclosure. For instance, mixtures of any of thepreviously mentioned anionic surfactants may be used. When two anionicsurfactants are present in a composition, those two surfactants will bepresent in relative amounts, based on the weight of each the surfactantsin the composition. For example, if the composition contains equalweights of the two anionic surfactants, then those two surfactants arepresent in a weight ratio of 1:1. If the composition contains twice asmuch of a first surfactant than of a second surfactant, then those twosurfactants are present in a weight ratio of 1:2. If the secondsurfactant is present within a range of permissible weights, relative tothe weight of the first surfactant, and that range is between “equal tothe weight of the first surfactant” and “twice as much as the weight ofthe first surfactant” such that those two surfactants are present in aweight ratio of 1:(1-2).

As mentioned above, in one embodiment the present disclosure providesfor the presence of two anionic surfactants in a composition. In variousembodiments, those two anionic surfactants may be present at any of thefollowing relative amounts: 1:1; 1:(1-5); 1:(1-10); 1:(1-15); 1:(1-20);1:(1-25); 1:(1-30); 1:(5-10); 1:(5-15); 1:(5-20); 1:(5-25); 1:(5-30);1:(10-15); 1:(10-20); 1:(10-25); 1:(10-30); 1:(15-20); 1:(15-25);1:(15-30); 1:(20-25); and 1:(25-30).

In one embodiment the present disclosure provides a material fabricationfluid, e.g., a metal cutting fluid concentrate composition, thatcontains 10-25 wt % of a first anionic surfactant, optionally asulfonate surfactant such as sodium dodecylbenzene sulfonate, optionally12-23 wt % or optionally 15-20 wt % of the first anionic surfactant;5-15 wt % of an amphoteric surfactant, optionally a betaine surfactantsuch as cocamidopropyl betaine, optionally 7-13 wt % or optionally 7-11wt % of the betaine surfactant; 1-10 wt % of a second anionicsurfactant, optionally a sulfate surfactant such as sodium laurethsulfate or sodium dodecyl sulfate, optionally 2-8 wt % or 3-7 wt % ofthe second anionic surfactant; up to about 5 wt % of an organic solvent,optionally a glycol ether such as ethylene glycol butyl ether,optionally 1-4 wt % or 2-3 wt % of glycol ether; 2-15 wt % of athickener such as a cellulosic thickener, e.g., hydroxyethyl cellulose,optionally 4-12 wt % or 6-10 wt % of the thickener; up to about 10 wt %of calcium chloride, optionally 2-7 wt % or 3-6 wt % of calciumchloride. Optionally the concentrate may contain a third anionicsurfactant, such as sodium octyl sulfate, in an amount of up to about 5wt %. Water will also be present in the concentrate. The totalnon-aqueous content of the concentrate is about 25-75 wt %, or about30-70 wt %, or about 35-55 wt %, or about 40-50 wt % (in the last casethe water content is 50-40 wt %).

In one embodiment, the present disclosure provides a compositionincluding a first anionic surfactant at a concentration of 0.1-0.3 wt %(i.e., 0.1-0.3 g of first anionic surfactant in 100 g of thecomposition, i.e., 1000-3000 ppm of first anionic surfactant), a secondanionic surfactant different from the first anionic surfactant at aconcentration of 0.01-0.10 wt % (i.e., 100-1000 ppm of second anionicsurfactant), an amphoteric surfactant at a concentration of 0.05-0.15,(i.e., 500-1500 ppm of amphoteric surfactant), and anti-rust agent at aconcentration of 0.1-0.3 wt % (i.e., 1000-3000 ppm of anti-rust agent).The composition optionally also contains thickening agent at aconcentration of 0.05-0.15 wt % (500-1500 ppm of thickening agent),and/or inorganic salt at a concentration of 0.01-0.1 wt % (100-1000 ppmof inorganic salt), and/or non-volatile organic solvent at aconcentration of 0.01-0.1 wt % (100-1000 ppm of non-volatile organicsolvent), and/or defoaming agent at a concentration of 0.05-0.2 wt %(i.e., 500-2000 ppm of defoaming agent). In one embodiment, thecomposition contains each of these components, i.e., each of firstanionic surfactant, second anionic surfactant, amphoteric surfactant,anti-rust agent, thickening agent, inorganic salt, non-volatiles organicsolvent and defoaming agent. In one embodiment, the composition containseach of these components, i.e., each of first anionic surfactant whichis a sulfonate-containing surfactant, second anionic surfactant which isa sulfate-containing surfactant, amphoteric surfactant which is abetaine-containing surfactant, anti-rust agent, thickening agent whichis a cellulosic thickening agent, inorganic salt, non-volatiles organicsolvent and defoaming agent. In one embodiment, the composition containseach of these components, i.e., each of first anionic surfactant whichis a sulfonate-containing surfactant, second anionic surfactant which isa sulfate-containing surfactant, amphoteric surfactant which is abetaine-containing surfactant, anti-rust agent which is sodium nitrite,thickening agent which is a hydroxyethyl cellulose, inorganic salt whichis calcium chloride, non-volatiles organic solvent which is ethyleneglycol butyl ether, and defoaming agent which is a silicone defoamingagent.

In one embodiment, the present disclosure provides a compositionincluding a first anionic surfactant at a concentration of about 0.2 wt% (i.e., about 0.2 g of first anionic surfactant in 100 g of thecomposition, i.e., about 2000 ppm of first anionic surfactant), a secondanionic surfactant different from the first anionic surfactant at aconcentration of about 0.05 wt % (i.e., about 500 ppm of second anionicsurfactant), an amphoteric surfactant at a concentration of about 0.09wt % (i.e., about 900 ppm of amphoteric surfactant), and anti-rust agentat a concentration of about 0.2 wt % (i.e., about 2000 ppm of anti-rustagent). The composition optionally also contains thickening agent at aconcentration of 0.05-0.15 wt % (500-1500 ppm of thickening agent) orabout 800 ppm thickening agent, and/or inorganic salt at a concentrationof 0.01-0.1 wt % (100-1000 ppm of inorganic salt) or about 400 ppminorganic salt, and/or non-volatile organic solvent at a concentrationof 0.01-0.1 wt % (100-1000 ppm of non-volatile organic solvent) or about200 ppm of non-volatile organic solvent, and/or defoaming agent at aconcentration of 0.05-0.2 wt % (i.e., 500-2000 ppm of defoaming agent)or about 1000 ppm of defoaming agent. In one embodiment, the compositioncontains each of these components, i.e., each of first anionicsurfactant, second anionic surfactant, amphoteric surfactant, anti-rustagent, thickening agent, inorganic salt, non-volatiles organic solventand defoaming agent. In one embodiment, the composition contains each ofthese components, i.e., each of first anionic surfactant which is asulfonate-containing surfactant, second anionic surfactant which is asulfate-containing surfactant, amphoteric surfactant which is abetaine-containing surfactant, anti-rust agent, thickening agent whichis a cellulosic thickening agent, inorganic salt, non-volatiles organicsolvent and defoaming agent. In one embodiment, the composition containseach of these components, i.e., each of first anionic surfactant whichis a sulfonate-containing surfactant, second anionic surfactant which isa sulfate-containing surfactant, amphoteric surfactant which is abetaine-containing surfactant, anti-rust agent which is sodium nitrite,thickening agent which is a hydroxyethyl cellulose, inorganic salt whichis calcium chloride, non-volatiles organic solvent which is ethyleneglycol butyl ether, and defoaming agent which is a silicone defoamingagent.

The following are some additional exemplary embodiments of thecompositions of the present disclosure, where metal cutting compositionand metal cooling composition are used interchangeably:

-   -   1) A metal cutting composition comprising water, a first        surfactant, a thickening agent such as a cellulosic thickening        agent, and an anti-rust agent.    -   2) A metal cutting composition comprising water, a first        surfactant, an inorganic salt such as calcium chloride, and an        anti-rust agent.    -   3) A metal cooling composition of any of embodiments 1-2 wherein        the first surfactant is an anionic surfactant.    -   4) The composition of any of embodiments 1-3 wherein the first        surfactant is an anionic surfactant comprising a sulfonate        group.    -   5) The composition of any of embodiments 1-4 wherein the first        surfactant is sodium dodecylbenzene sulfonate.    -   6) The composition of any of embodiments 1-5 comprising a second        surfactant, wherein the second surfactant is an amphoteric        surfactant.    -   7) The composition of any of embodiments 1-6 comprising a second        surfactant, wherein the second surfactant is an amphoteric        surfactant comprising a betaine group.    -   8) The composition of any of embodiments 1-7 comprising a second        surfactant, wherein the second surfactant is cocamidopropyl        betaine.    -   9) The composition of any of embodiments 1-8 comprising a third        surfactant, wherein the third surfactant is an anionic        surfactant.    -   10) The composition of any of embodiments 1-9 comprising a third        surfactant, wherein the third surfactant is an anionic        surfactant comprising a sulfate group.    -   11) The composition of any of embodiments 1-10 comprising a        third surfactant, wherein the third surfactant is sodium laureth        sulfate.    -   12) The composition of any of embodiments 1-11 wherein the        anti-rust agent is sodium nitrite.    -   13) The composition of any of embodiments 1-12 comprising a        thickening agent which is a cellulosic thickening agent, wherein        the cellulosic thickening agent is hydroxyl ethyl cellulose.    -   14) The composition of any of embodiments 1-13 comprising a        defoaming agent.    -   15) The composition of any of embodiments 1-14 comprising a        defoaming agent, wherein the defoaming agent is a silicone        polymer.    -   16) The composition of any of embodiments 1-15 comprising a        first surfactant that comprises a sulfonate group and a second        surfactant that comprises a sulfate group.

As discussed below, the present disclosure also provides a method ofmachining metal, comprising applying a composition comprising acomposition of any of embodiments 1-16 to a piece of metal beingmachined, in an amount and time that are effective to dissipate heatfrom the metal being machined. The machining process may achieve cuttingof the metal, and thus be referred to as a cutting process. Themachining process may be any of broaching, tapping, hobbing, cutting,drilling, milling, turning, sawing, honing or grinding, which areexamples of the machining processes that may be used in the method ofthe present disclosure.

The following are some additional exemplary embodiments of thecompositions of the present disclosure. A composition comprising water,a first surfactant, a thickening agent, and an anti-rust agent. Thefirst surfactant may be an anionic surfactant, such as a sulfonate- orsulfate-containing surfactant. Optionally, the first surfactant issodium dodecylbenzene sulfonate. Optionally, the first surfactant issodium laureth sulfate. Rather than being an anionic surfactant, thefirst surfactant may be an amphoteric surfactant, such as abetaine-containing surfactant, e.g., cocamidopropyl betaine. Optionally,the composition may include two surfactants, where each is an anionicsurfactant, e.g., wherein the two surfactants are a sulfate-containingsurfactant and a sulfonate-containing surfactant such as sodium laurethsulfate and sodium dodecylbenzene sulfonate. Optionally, the compositionmay include two surfactants, where one is an anionic surfactant and theother is an amphoteric surfactant, such as a sulfate-containing anionicsurfactant and a betaine-containing amphoteric surfactant where thesulfate-containing anionic surfactant may be sodium laureth sulfate andthe betaine-containing amphoteric surfactant may be cocamidopropylbetaine. Optionally, the composition may include two surfactants, whereone is an anionic surfactant and the other is an amphoteric surfactant,such as a sulfonate-containing anionic surfactant and abetaine-containing amphoteric surfactant, where the sulfonate-containinganionic surfactant may be sodium dodecylbenzene sulfonate and thebetaine-containing amphoteric surfactant may be cocamidopropyl betaine.Optionally, the composition may include three surfactants, two of thethree surfactants being non-identical anionic surfactants and one of thethree surfactants being an amphoteric surfactant, where these threesurfactants may optionally be a sulfate-containing surfactant, asulfonate-containing surfactant, and a betaine-containing surfactant,e.g., sodium dodecylbenzene sulfonate, sodium laureth sulfate, andcocamidopropyl betaine. When present, the sulfonate-containingsurfactant may be present at a concentration of about 1800 ppm, e.g.,1000-3000 ppm. When present, the sulfate-containing surfactant may bepresent at a concentration of about 500 ppm, e.g., 100-1000 ppm. Whenpresent, the amphoteric surfactant may be present at a concentration ofabout 900 ppm, e.g., 500-1500 ppm. The composition will contain aneffective amount of an anti-rust agent as described herein, where theanti-rust agent may be, e.g., sodium nitrite. The concentration of theanti-rust agent may be about 100-5000 ppm, or about 1000-3000 ppm, orabout 2000 ppm. The thickening agent is described herein, and may be,e.g., a cellulosic thickening agent such as hydroxyl ethyl cellulose.The concentration of the thickening agent in the composition may beabout 100-2000 ppm, or about 500-1500 ppm, or about 800 ppm. Thecomposition may optionally contain, and in one embodiment does contain,a defoaming agent as described herein. An exemplary defoaming agent is asilicone polymer. When present, the defoaming agent may be present at aconcentration of about 100-5000 ppm, or about 500-2000 ppm, or about1000 ppm.

The following are some additional exemplary embodiments of thecompositions of the present disclosure. A composition comprising water,a first surfactant, an inorganic salt, and an anti-rust agent. The firstsurfactant may be an anionic surfactant, such as a sulfonate- orsulfate-containing surfactant. Optionally, the first surfactant issodium dodecylbenzene sulfonate. Optionally, the first surfactant issodium laureth sulfate. Rather than being an anionic surfactant, thefirst surfactant may be an amphoteric surfactant, such as abetaine-containing surfactant, e.g., cocamidopropyl betaine. Optionally,the composition may include two surfactants, where each is an anionicsurfactant, e.g., wherein the two surfactants are a sulfate-containingsurfactant and a sulfonate-containing surfactant such as sodium laurethsulfate and sodium dodecylbenzene sulfonate. Optionally, the compositionmay include two surfactants, where one is an anionic surfactant and theother is an amphoteric surfactant, such as a sulfate-containing anionicsurfactant and a betaine-containing amphoteric surfactant where thesulfate-containing anionic surfactant may be sodium laureth sulfate andthe betaine-containing amphoteric surfactant may be cocamidopropylbetaine. Optionally, the composition may include two surfactants, whereone is an anionic surfactant and the other is an amphoteric surfactant,such as a sulfonate-containing anionic surfactant and abetaine-containing amphoteric surfactant, where the sulfonate-containinganionic surfactant may be sodium dodecylbenzene sulfonate and thebetaine-containing amphoteric surfactant may be cocamidopropyl betaine.Optionally, the composition may include three surfactants, two of thethree surfactants being non-identical anionic surfactants and one of thethree surfactants being an amphoteric surfactant, where these threesurfactants may optionally be a sulfate-containing surfactant, asulfonate-containing surfactant, and a betaine-containing surfactant,e.g., sodium dodecylbenzene sulfonate, sodium laureth sulfate, andcocamidopropyl betaine. When present, the sulfonate-containingsurfactant may be present at a concentration of about 1800 ppm, e.g.,1000-3000 ppm. When present, the sulfate-containing surfactant may bepresent at a concentration of about 500 ppm, e.g., 100-1000 ppm. Whenpresent, the amphoteric surfactant may be present at a concentration ofabout 900 ppm, e.g., 500-1500 ppm. The composition will contain aneffective amount of an anti-rust agent as described herein, where theanti-rust agent may be, e.g., sodium nitrite. The concentration of theanti-rust agent may be about 100-5000 ppm, or about 1000-3000 ppm, orabout 2000 ppm. The inorganic salt is described herein, and may be, forexample, calcium chloride. The concentration of the inorganic salt inthe composition may be about 50-2000 ppm, or about 100-1000 ppm, orabout 400 ppm. The composition may optionally contain, and in oneembodiment does contain, a defoaming agent as described herein. Anexemplary defoaming agent is a silicone polymer. When present, thedefoaming agent may be present at a concentration of about 100-5000 ppm,or about 500-2000 ppm, or about 1000 ppm.

Methods of Manufacture

In one aspect, the present disclosure provides methods of preparing thematerial fabrication fluid, e.g., the metal cutting fluid concentratecompositions and the corresponding metal cutting fluid compositions asidentified herein. In general, the concentrates are prepared bycombining water with one or more surfactants selected from anionic andamphoteric surfactants, along with optional ingredients. Thecompositions are prepared by diluting the concentrate with water oraqueous solution.

In one embodiment, a concentrate is prepared by combining a firstsurfactant which is an amphoteric surfactant, a second surfactant whichis an anionic surfactant, and a third surfactant selected from anamphoteric and an anionic surfactants, where the third surfactant isother than the first or second surfactants. The concentrate mayoptionally contain additional surfactant(s), i.e., a fourth, fifth, etc.surfactant. In addition, or alternatively, the concentrate may containactive ingredient(s) other than surfactant, e.g., inorganic components,organic solvents and thickening agents. The compositions are waterbased, in other words, they are aqueous compositions in that the carrieris primarily water. The compositions may be prepared by any of thefollowing methods.

In one embodiment, a container of water is provided. This containerholds between about 5 and 20 Kg of water. This method may be scaled upor down so as to provide the desired amount of fluid concentrate. Theinitial amount of water is about 5-40%, or about 10-30% of the totalamount of water in the concentrate. The water may be at ambienttemperature or it may be at an elevated temperature. Elevatedtemperatures of below the boiling point of water, i.e., below 100° C.,or below 90° C., or below 80° C., or below 70° C. may be used. Elevatedtemperatures in excess of the ambient temperature, e.g., above 25° C.,or above 30° C., or above 40° C., or above 50° C., or above 60° C., orabove 70° C. may be used.

The one or more surfactants are then added to the water. In oneembodiment an amphoteric surfactant is added to the water, followed bythe sequential addition of a first and second anionic surfactant. In analternative embodiment, an anionic surfactant is added first to thewater, followed by an amphoteric surfactant, which in turn is followedby the addition of either a second anionic surfactant or a secondamphoteric surfactant. In another embodiment, the first and secondanionic surfactants are added sequentially, followed by the addition ofan amphoteric surfactant.

After the addition of a surfactant to the water, the resulting mixtureis stirred to provide a homogeneous or near homogeneous state. Stirringmay be performed leisurely or vigorously, however in either event it ispreferred that undue amounts of foam are not created. Foam typicallyresults from the entrapment of air in the mixture, where air tends tobecome entrapped when there is a significant vortex created during themixing process and/or when the stirring device repeated enters and exitsthe mixture. Foam retention also tends to be greater when the viscosityof the mixture is greater. These situations are preferably avoided inorder to minimize foam production. In order to assure good mixing, astirring time of about 15-60 minutes may be employed after the additionof each surfactant.

Depending on the presence or absence of insulation surrounding thecontainer in which the concentrate is being prepared, the temperature ofthe mixture may drop during the surfactant addition and stirring steps.Alternatively, the temperature of the mixture may be maintained at ornearly at the original temperature of the water by, for example,maintaining gentle heating directed to the sides and/or the bottom ofthe container which holds the concentrate. Alternatively, oradditionally, heating coils may be positioned within the container toadd or withdraw heat from the concentrate as desired.

As surfactant is added to the water, the viscosity of the mixture willtend to increase. A solution of increased viscosity will tend to entrapair more readily than does a lower viscosity solution, all other factorsbeing equal. In order to reduce the viscosity of a mixture, additionalwater may be added to the mixture after the addition of any of thefirst, second or third surfactants. For example, an amount of waterwhich is about 5-40%, or about 10-30% of the total amount of water inthe concentrate may be added to the mixture after the first addition ofsurfactant. In addition, or alternatively, an amount of water which isabout 5-40%, or about 10-30% of the total amount of water in theconcentrate may be added to the mixture after the second addition ofsurfactant.

After all of the surfactants have been added and thoroughly mixed intothe water, optional ingredient(s) may be added to the resulting mixture.For example, an inorganic component, e.g., an inorganic salt, may beadded to the mixture, followed by stirring to completely dissolve theinorganic component. The optional ingredient(s) may be added to the warmor hot mixture, or to the mixture after it has cooled down to roomtemperature. Since the concentrate will typically be stored and used atroom temperature, any optional ingredients that will significantlyimpact the viscosity or flow properties of the mixture are typicallyadded to the mixture at room temperature.

The surfactants and optional ingredients may be added to the water in aneat form, i.e., without being in contact with a solvent, or may beadded in a diluted form, i.e., in contact with a solvent so as toprovide a solution, paste, dispersion, etc. of the ingredient. In oneembodiment, the surfactants are added to water in the order of theirsolids content in water, with the more concentrated ingredient beingadded first. In other words, if a surfactant is at 50% solids andanother surfactant is at 25% solids, then the surfactant at 50% solidsis added to water before the surfactant at 25% solids is added to themixture.

The concentrate may be prepared in a batch, continuous orsemi-continuous mode. In a batch mode, ingredients are addedsequentially to a container of water, until all of the ingredients havebeen added, in which case a batch of concentrate has been prepared. In acontinuous mode, water is propelled through a pipe or other conduit, andvarious ingredients are added to the water at various points along theconduit. For example, the conduit may be fitted with T-valves, where aningredient may be fed into the water, or aqueous mixture, through theT-valve. The conduit may also contain mixers within the conduit, eitherstatic or inline mixers, to facilitate the creation of a homogenousmixture after an ingredient has been added to the water or aqueousmixture. For example, water and a first surfactant may be fed into apipe and pass through a mixer. Typically a static mixer is adequate ifthe surfactant is pre-dissolved in water. Otherwise, an inline mixer istypically preferred. Thereafter, a second surfactant is added to theconduit downstream of the mixer, which again goes through a mixingprocess. Finally, a third surfactant is added to the aqueous mixture,following by mixing as needed, so as to provide an aqueous mixturecomprising three surfactants. Thereafter, additional, optionalingredients may be added to the conduit, through a T-valve for example,following by suitable stirring, to form the final concentrate.

To facilitate mixing of the various ingredients, and to minimize vortexformation and consequently foam formation, baffles may be installedwithin the batch or continuous reactor. Suitable mixing equipment, suchas agitators, impellers, static mixers, colloid mills, and homogenizersare made and sold by, e.g., Chemineer (Dayton, Ohio) and Sulzer(Winterthur, Switzerland).

In an alternative embodiment for a continuous process, three T-valvesare located at the beginning of the conduit, at a location after waterhas already been added to the conduit. The first, second and thirdsurfactants are each delivered into the conduit through one of the threeT-valves. In this manner, all of the three surfactants are combinedessentially at the same time, and then the resulting mixture is passedthrough an inline or static mixer within the conduit, to provide ahomogenous aqueous mixture. Optional ingredients are then added to thehomogeneous aqueous mixture as desired, to provide the finalconcentrate.

In either a continuous or batch process, the water and/or aqueousmixture may be heated to a temperature in excess of ambient temperature,e.g., a temperature between 50° C. and 90° C. Heating may beaccomplished by routine methods known in the art. The elevatedtemperature may be maintained as needed to facilitate prompt mixing ofthe ingredients to form a homogeneous mixture.

Accordingly, in one embodiment, the present disclosure provides acontinuous process for making a material fabrication fluid, e.g., ametal cutting fluid concentrated composition. The process comprisesproviding a continuous reactor, charging water to the continuousreactor, adding to the water in the continuous reactor the desired oneor more surfactants, e.g., a) a first anionic surfactant, b) a secondamphoteric surfactant, and c) a third surfactant selected from ananionic surfactant and a cationic surfactant, the third surfactant beingdifferent from the first surfactant and the second surfactant; andmixing components a), b) and c) to provide a homogeneous mixture.Optionally, the continuous reactor is maintained at a temperature inexcess of 50° C. Also optionally, a mixer selected from an in-line mixerand a static mixer is present in the continuous reactor.

Method of Use

The present disclosure provides fabrication fluids, e.g., fluids usefulin metal cutting, that may be used in the course of materialsfabrication, e.g., cutting metal. In one embodiment, the fluidconcentrate of the present disclosure is diluted with water to provide acomposition that may be applied to tooling involved in materialfabrication, e.g., a metal cutting fluid composition that is applieddirectly to the metal. The concentrate will have a solids level orcontent, measured as the sum of the weights of the non-aqueouscomponents in the concentrate, divided by the total weight of theconcentrate. When water is combined with concentrate so as to form ametal cutting fluid composition, the metal cutting fluid compositionwill likewise have a solids level or content, which will be less thanthe solids level or content of the concentrate. In various embodiment,the composition is formed by combining sufficient water with theconcentrate so as to provide a metal cutting fluid composition having aweight percent solids, based on the total weight of composition, of0.1%, or 0.5%, or 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%, or 4%, or4.5% or 5% or 5.5% or 6% or 65% or 7% or 7.5% or 8% or 8.5% or 9% or9.5% or 10%, or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or13.5%, or 14%, or 14.5%, or 15%, or 15.5%, or 16%, or 16.5%, or 17%, or17.5%, or 18%, or 18.5%, or 19%, or 20%, or a concentration within arange provided any of the two aforesaid solids percent values, e.g.,0.5% to 4%.

In one aspect, the prepared person will have a supply of metal cuttingfluid concentrate in storage, readily available when needed to cutmetal, and with access to a method of combining the concentrate withwater so as to form a metal cutting fluid composition. Optionally, themetal cutting fluid concentrations as disclosed herein may be dilutedwith water to create a metal cutting fluid composition.

Cutting fluid maintenance involves checking the concentration of solubleoil emulsions (using refractometers), pH (using a pH meter), thequantity of tramp oil (hydraulic oil leaking into the cutting fluidsystem) and the quantity of particulates in the fluid. Action taken tomaintain the fluid includes adding make-up concentrate or water,skimming of tramp oil, adding biocides to prevent bacterial growth andfiltering the particulates by centrifuging.

The cutting fluid within a coolant system degrades with time due tobacterial growth and contamination with tramp oil and fine metal swarffrom the machining operation. When it becomes uneconomical to maintainthe fluid by regular make-up operations it is dumped. Prior to lettingthe fluid flow into a sewer system, it should be treated to bring thefluid composition to safe disposal levels.

Some metals are more difficult to machine than others. Stainless steel,exotic alloys and very hard metals demand a very high level ofperformance from the cutting fluid. Other metals, like brass andaluminum, are easy to machine with general-purpose oils. Where tough,low-machinability metals are involved, it is advantageous to use highlyadditized cutting oil with excellent extreme-pressure (EP) and anti-weldcapability. Most often, these oils contain active sulfur and chlorine toprotect the tooling and ensure good parts finish. In one embodiment, thecutting fluid of the present invention include active sulfur and/orchlorine.

For brass, aluminum, many carbon steels and low-alloy steels, a cuttingoil with lubricity additives, friction modifiers and mild EP/anti-weldperformance is sufficient. These oils are generally formulated withsulfurized fat (inactive) and/or chlorinated paraffin. Active cuttingoils (containing active sulfur) should not be used for brass andaluminum, as they will stain or tarnish the finished parts. Oilsformulated for brass and aluminum are often called “non-staining” oils.In one embodiment, the cutting fluid of the present invention includesone or more of lubricity additives, friction modifiers, sulfurized fat(inactive) and chlorinated paraffin.

Easy machining operations (turning, forming, drilling, milling, etc.)can be performed at higher speeds and require high levels of coolingwith only modest EP capability. The milder operations can be performedwith lower viscosity, lightly additized fluids. Difficult machiningoperations must be run at lower speeds and require a great deal ofanti-weld protection. Oils designed specifically for the most difficultoperations, like thread-cutting or broaching, are generally higher inviscosity and loaded with EP additives like active sulfur and chlorine.

The type of machinery will also dictate some of the cutting oilcharacteristics. For example, screw machines experience heavycross-contamination between the lube oil and cutting oil. For thisreason, these machines frequently run on dual-purpose or tri-purposeoils that can be used in the lube boxes, hydraulics and cutting oilsumps.

Grinders, gun drills and deep-hole drilling machines require lighterviscosity oils for high rates of cooling, good chip and swarf flushing,through-the-tool delivery and high-pressure application without foaming.CNC OEMs may place restrictions on the cutting oil due to potentialincompatibility between the cutting fluid and machine components, suchas seals. Centerless grinders may require a tougher fluid than surfacegrinders.

In general, the compositions of the present disclosure, in aready-to-use form, may be applied during a material fabrication process.As used herein, material fabrication, which may also be referred to asmachining, is a process whereby a tool makes contact with, and is usedto modify the shape or surface of, a material by any suitable method,and heat is generated at the contact point between the material and thetooling. Examples include cutting into the material with a blade,drilling a hole in the material with a drill bit, and removing a surfacelayer of the material with a lathe. Another example of materialfabrication is stamping. The composition may be applied to the materialbeing fabricated and/or the tooling that comes into contact with thematerial being fabricated. Examples of the application process includeflooding, spraying, dripping, misting, and brushing the composition ontothe part being fabricated and/or the associated tooling that contactsthe part being fabricated. The material being fabricated may be, forexample, metal, stone or plastic. The composition, after application,will maintain the tooling/material interface at a relatively cooltemperature so that harm, e.g., warpage, is avoided for each of thematerial being fabricated and the tooling doing the fabricating. Thecomposition may also provide lubricating properties.

For example, when the fabrication fluid is a metal cutting fluid, thefluid provides coolant and lubricant properties as need for metalworking processes, such as machinery and stamping. Metal cuttinggenerates heat due to friction, which can deform the material. Coolantswork to remove the heat from the machinery and materials so it can speedthe cutting process, making the machines more productive. Besidescooling, cutting fluids also aid the cutting process by lubricating theinterface between the tool's cutting edge and the chip. By preventingfriction at this interface, some of the heat generation is prevented.This lubrication also helps prevent the chips from being welded onto thetool, which would interfere with subsequent cutting. Most metal workingand machining processes can benefit from the use of cutting fluids,depending on the workpiece material.

The compositions of the present disclosure provide one or more of thefollowing benefits in materials fabrication: keeping the workpiece at astable temperature (which is critical when working to close tolerances);maximizing the lifetime of the cutting tip by lubricating the workingedge and reducing the top welding; ensuring safety for the peoplehandling it (toxicity, bacteria, and fungi) and for the environment upondisposal; and preventing rust on machine parts and cutters.

A portion of the fabricating equipment will come into contact with theworkpiece being fabricated. For example, the fabricating equipment mayhave a blade that cuts the material during fabrication. The blade may bemetal, e.g., stainless steel, or it may be diamond encrusted.Alternatively, the fabricating equipment may be a turning tool such as alatche or a drill, or a polishing or sanding device.

Thus, the present disclosure provides methods of delivering afabrication fluid, e.g., a metal cooling composition, as describedherein. In one embodiment, the present disclosure provides a methodcomprising providing a fabrication composition of the presentdisclosure, applying that composition to one or both of the materialbeing fabricated and the tooling that is being used to fabricate thematerial, and fabricating the material with the tooling in the presenceof the composition of the present disclosure. The method affords coolingand temperature control at the interface where the tooling contact thefabricated material, and/or provides lubrication at that interface.

For example, the present disclosure provides a method for fabricating asolid material such as metal, stone, plastic, the method comprisingproviding a composition of the present disclosure, such as a compositioncomprising water, a first surfactant, a thickening agent, and ananti-rust agent; applying that composition to the material beingfabricated, e.g., by brushing, spraying, or pouring the composition ontothe material and/or onto the tooling that does the fabricating, wherethe composition will transfer to the interface of the tooling/materialduring the fabrication process; and fabricating that material withtooling in the presence of the composition.

As another example, the present disclosure provides a method forfabricating a solid material such as metal, stone, plastic, the methodcomprising providing a composition of the present disclosure, such as acomposition comprising water, a first surfactant, an inorganic salt, andan anti-rust agent; applying that composition to the material beingfabricated, e.g., by brushing, spraying, or pouring the composition ontothe material and/or onto the tooling that does the fabricating, wherethe composition will transfer to the interface of the tooling/materialduring the fabrication process; and fabricating that material withtooling in the presence of the composition.

The stone may be, for example, any of granite, limestone, marble,sandstone, slate, basalt, tavertine or quartzite. Other stones may alsobe fabricated using the compositions of the present disclosure.

The plastic may be, for example, a pure polymer such as polypropyleneand polyethylene, or a plastic composite, such as a composite of polymerand stone, e.g., CORIAN™. The plastic may be a silicon chip or othersilicon product such as a silicon wafer or other silicon material usedin the semiconductor industry.

The composition and methods of use thereof according to the presentdisclosure achieve one or both of a) a reduction in the heat beinggenerated on the cutting surface to improve the quality of the product(e.g., fewer burrs, smoother cut, less deformation (in the case ofplastic); and b) increasing the longevity of the fabricating device. Inone embodiment, the compositions of the present disclosure containlittle or no oil, and accordingly their use eliminates the problem ofdisposing of toxic oil-based waste that is associated with alternativefabricating fluids.

The following examples are provided to illustrate embodiments of thepresent disclosure and are not to be construed as limiting thereon.

EXAMPLES

In the following examples, the indicated commercial products may nothave the solids content or the neutralization indicated as being used inthe example. In such a case, the commercial product may be diluted withwater to the indicted solids content and/or neutralized with acid orbase as needed to provide the indicated neutralized form. The thickeningagent is added to provide a final viscosity approximately that of wholemilk or orange juice.

Example 1

To about 10 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 9 kg at about60% solids in water of branched chain sodium dodecylbenzene sulfonate,e.g., SULFONIC 100 from Stepan Company, after neutralization with sodiumhydroxide), amphoteric surfactant solution (about 4.5 kg at about 35%solids in water of cocamidopropylbetaine, e.g., AMPHOSOL CA from StepanCompany), heated water (about 9 kg), second anionic surfactant solution(about 11 kg at about 3% solids in water of sodium lauryl ether sulfate,e.g., CALFOAM ES-703 from Pilot Chemical Co.), and inorganic saltsolution (about 2 kg at about 30% solids in water of calcium chloride,where calcium chloride in both solid and solution forms is availablefrom e.g., OxyChem, Ludington, Mich.). The resulting mixture is allowedto cool to ambient temperature (about 8 hours) and then thickening agent(about 4 kg of about 1.5% solids in water of sodium carboxy methylcellulose, e.g., AQUALON, Ashland Chemicals, Covington, Ky.) is added.To this mixture is added a desired amount of anti-rust agent, andoptionally further added are one or both of defoamer and colorant, toprovide the final metal cutting fluid concentrate.

Example 2

To about 10 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 9 kg at about53% solids in water of triethanolamine dodecylbenzene sulfonate, CALSOFTT60 (Pilot Chemical), amphoteric surfactant solution (about 4.5 kg atabout 35% solids in water of sodium cocoamphoacetate, AMPHITOL 20Y-B(Kao Chemicals), heated water (about 6.5 kg), second anionic surfactantsolution (about 14 kg at about 7% solids in water of ammonium laurylsulfate, EMAL AD-25R (Kao Chemicals)), and inorganic salt solution(about 2 kg at about 30% solids in water of calcium chloride, wherecalcium chloride in both solid and solution forms is available frome.g., OxyChem, Ludington, Mich.). The resulting mixture is allowed tocool to ambient temperature (about 8 hours) and then thickening agent(about 4 kg of about 1.5% solids in water of sodium carboxy methylcellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture isadded a desired amount of anti-rust agent, and optionally further addedare one or both of defoamer and colorant, to provide the final cuttingfluid concentrate.

Example 3

To about 8 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 8.5 kg at about53% solids in water of sodium lauryl sulfoacetate, LATHANOL LAL flake(Stepan Co.), amphoteric surfactant solution (about 6.3 kg at about 30%solids in water of lauryl hydroxysultaine, AMPHITOL 20HD, KaoChemicals), heated water (about 6.5 kg), second anionic surfactantsolution (about 14 kg at about 7% solids in water of sodium octyl phenolethoxylate sulfate, POE-3, POLY-STEP C-OP3S (Stepan Co.)), and inorganicsalt solution (about 2 kg at about 30% solids in water of calciumchloride, where calcium chloride in both solid and solution forms isavailable from e.g., OxyChem, Ludington, Mich.). The resulting mixtureis allowed to cool to ambient temperature (about 8 hours) and thenthickening agent (about 4 kg of about 1.5% solids in water of sodiumcarboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals, Covington,Ky.) is added. To this mixture is added a desired amount of anti-rustagent, and optionally further added are one or both of defoamer andcolorant, to provide the final cutting fluid concentrate.

Example 4

To about 8.5 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 9 kg at about53% solids in water of polyoxyethylene (10) nonylphenol phosphate,FOSFODET 9Q/22 (Kao Chemicals)), amphoteric surfactant solution (about5.3 kg at about 35% solids in water of disodium cocoamphodipropionate,CRODATERIC CADP 38 (Croda)), heated water (about 6 kg), second anionicsurfactant solution (about 14 kg at about 7% solids in water of sodiumdioctyl sulfosuccinate, STEPWET DOS-70 (Stepan Co.)), and inorganic saltsolution (about 3.3 kg at about 30% solids in water of calcium chloride,where calcium chloride in both solid and solution forms is availablefrom e.g., OxyChem, Ludington, Mich.). The resulting mixture is allowedto cool to ambient temperature (about 8 hours) and then thickening agent(about 4 kg of about 1.5% solids in water of sodium carboxy methylcellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture isadded a desired amount of anti-rust agent, and optionally further addedare one or both of defoamer and colorant, to provide the final cuttingfluid concentrate.

Example 5

To about 15 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 5 kg at about53% solids in water of polyoxyethylene (8) octyl ether carboxylic acid,AKYPO LF2 (Kao Chemical)), amphoteric surfactant solution (about 8.3 kgat about 30% solids in water of cocamidopropylamine oxide, CALOXAMINECPO (Pilot Chemical)), heated water (about 14 kg), second anionicsurfactant solution (about 7.5 kg at about 20% solids in water of sodiumlauroyl sarcosinate, MAPROSYL 30-B (Stepan Co.)), and inorganic saltsolution (about 3.3 kg at about 30% solids in water of calcium chloride,where calcium chloride in both solid and solution forms is availablefrom e.g., OxyChem, Ludington, Mich.). The resulting mixture is allowedto cool to ambient temperature (about 8 hours) and then thickening agent(about 4 kg of about 1.5% solids in water of sodium carboxy methylcellulose, e.g., AQUALON, Ashland Chemicals, Covington, Ky.) is added.To this mixture is added a desired amount of anti-rust agent, andoptionally further added are one or both of defoamer and colorant, toprovide the final cutting fluid concentrate.

Example 6

To about 14 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 5.6 kg at about50% solids in water of potassium oleate, ICTEOL K-50 (Kao Chemicals)),amphoteric surfactant solution (about 8.3 kg at about 30% solids inwater of cocamidopropyl betaine, CALTAINE C-35 (Pilot Chemical), heatedwater (about 15 kg), second anionic surfactant solution (about 6 kg atabout 20% solids in water of disulfonated diphenyl oxide with lineardecyl substitution, DOWFAX C1OL, (Dow Chemical)), and inorganic saltsolution (about 3.3 kg at about 30% solids in water of calcium chloride,where calcium chloride in both solid and solution forms is availablefrom e.g., OxyChem, Ludington, Mich.). The resulting mixture is allowedto cool to ambient temperature (about 8 hours) and then thickening agent(about 4 kg of about 1.5% solids in water of sodium carboxy methylcellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture isadded a desired amount of anti-rust agent, and optionally further addedare one or both of defoamer and colorant, to provide the final cuttingfluid concentrate.

Example 7

To about 15 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 5 kg at about50% solids in water of isopropylamine dodecylbenzene sulfonate, NINATE411 (Stepan Co.)), amphoteric surfactant solution (about 10 kg at about30% solids in water of cocamidopropyl hydroxysultaine, AMPHOSOL CS-50(Stepan), heated water (about 15 kg), second anionic surfactant solution(about 5 kg at about 30% solids in water of sodium dodecylbenzenesulfonate, MELIOSOL 50X (Kao Chemical), and inorganic salt solution(about 3.3 kg at about 30% solids in water of calcium chloride, wherecalcium chloride in both solid and solution forms is available frome.g., OxyChem, Ludington, Mich.). The resulting mixture is allowed tocool to ambient temperature (about 8 hours) and then thickening agent(about 4 kg of about 1.5% solids in water of sodium carboxy methylcellulose, e.g., AQUALON, Ashland Chemicals, Covington, Ky.) is added.To this mixture is added a desired amount of anti-rust agent, andoptionally further added are one or both of defoamer and colorant, toprovide the final cutting fluid concentrate.

Example 8

To about 20 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 8.4 kg at about50% solids in water of disulfonated diphenyloxide with alkylsubstitution, DOWFAX C1OL (Dow Chemical)), amphoteric surfactantsolution (about 6.7 kg at about 30% solids in water oflauramidopropylbetaine, AMPHITOL 20AB (Kao Chemicals), heated water(about 12 kg), second anionic surfactant solution (about 4 kg at about20% solids in water of sodium C14-C16 olefin sulfonate, ALFANOX 46 (KaoChemical), and inorganic salt solution (about 1.7 kg at about 30% solidsin water of calcium chloride, where calcium chloride in both solid andsolution forms is available from e.g., OxyChem, Ludington, Mich.). Theresulting mixture is allowed to cool to ambient temperature (about 8hours) and then thickening agent (about 4 kg of about 1.5% solids inwater of sodium carboxy methyl cellulose, e.g., WALOCEL CRT, DowChemical) is added. To this mixture is added a desired amount ofanti-rust agent, and optionally further added are one or both ofdefoamer and colorant, to provide the final cutting fluid concentrate.

Example 9

To about 10 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 9 kg at about60% solids in water of linear chain sodium dodecylbenzene sulfonate,e.g., CALSOFT F90 (Pilot Chemical)), amphoteric surfactant solution(about 4.5 kg at about 35% solids in water of cocamidopropylbetaine,e.g., AMPHOSOL CA from Stepan Company), heated water (about 9 kg),second anionic surfactant solution (about 11 kg at about 3% solids inwater of sodium lauryl ether sulfate, e.g., CALFOAM ES-703 from PilotChemical Co.), and inorganic salt solution (about 2 kg at about 30%solids in water of calcium chloride, where calcium chloride in bothsolid and solution forms is available from e.g., OxyChem, Ludington,Mich.). The resulting mixture is allowed to cool to ambient temperature(about 8 hours) and then thickening agent (about 4 kg of about 1.5%solids in water of sodium carboxy methyl cellulose, e.g., AQUALON,Ashland Chemicals, Covington, Ky.) is added. To this mixture is added adesired amount of anti-rust agent, and optionally further added are oneor both of defoamer and colorant, to provide the final cutting fluidconcentrate.

Example 10

To about 10 kg of heated water (about 75° C.) is sequentially added thefollowing ingredients, each ingredient addition being followed bystirring for a period of about 30 minutes in a manner that minimizesfoam formation: first anionic surfactant solution (about 9 kg at about60% solids in water of linear chain sodium dodecylbenzene sulfonate,e.g., CALSOFT F90 (Pilot Chemical)), amphoteric surfactant solution(about 4.5 kg at about 35% solids in water of cocamidopropyl betaine,e.g., AMPHOSOL CA from Stepan Company), heated water with dissolvedethylene glycol butyl ether (about 9 kg water and about 1 kg ether),second anionic surfactant solution (about 11 kg at about 3% solids inwater of sodium laureth sulfate, e.g., CALFOAM ES-703 from PilotChemical Co.), and inorganic salt solution (about 2 kg at about 30%solids in water of calcium chloride, where calcium chloride in bothsolid and solution forms is available from e.g., OxyChem, Ludington,Mich.). The resulting mixture is allowed to cool to ambient temperature(about 8 hours) and then thickening agent (about 4 kg of about 1.5%solids in water of sodium carboxy methyl cellulose, e.g., AQUALON,Ashland Chemicals, Covington, Ky.) is added. To this mixture is added adesired amount of anti-rust agent, and optionally further added are oneor both of defoamer and colorant, to provide the final cutting fluidconcentrate.

Example 11

The present disclosure provides cutting fluids of high solids content(also referred to as high solids centration), which are calledconcentrates (or cutting fluid concentrates), and which may be dilutedwith water prior to being used in a machining or fabricating operation.Table 1 identifies various machining operations characterized by themetal being machined and the process being applied to the metal. Theprocesses are exemplary of the processes used in metal working, such asbroaching, tapping, hobbing, cutting, drilling, milling, turning,sawing, honing and grinding. Each of these processes benefits from theapplication of cutting fluid to the metal during the metal working ormachining process, where the desired amount of cutting fluid depends notonly on the specific process, but also on the identity of the metalbeing subjected to the process. In addition to identifying variousprocesses, Table 1 identifies 8 common metals, namely, aluminum (Al)alloy, brass, casting iron (also known as cast iron), bronze, low carbonsteel, stainless steel, alloy steel and titanium (Ti) alloy. For eachprocess and metal selected, Table 1 indicates the parts of water thatmay be added to 1 part of a cutting fluid concentrate of the presentdisclosure in order to create an effective cutting fluid. For example,bronze may be broached using a cutting fluid prepared from 10 parts ofwater and 1 part of cutting fluid concentrate of the present disclosure.As another example, titanium alloy may be turned using a cutting fluidprepared by combining anywhere from between 5 to 10 parts of water foreach 1 part of cutting fluid concentrate of the present disclosure.

TABLE 1 Low- Stain- Al Casting Carbon less Alloy Ti Process alloy BrassIron Bronze Steel Steel Steel Alloy Broaching 10-15 10-15 10 10 10 5 5 5Tapping 10-15 10-15 10 10 10 5 5 5 Hobbing 10-15 10-15 10 10 10 5 5 5Cutting 10-15 10-15 10-15 10-15 10-15 5-10 5-10 5 Drilling 10-15 10-1510-15 10-15 10-15 5-10 5-10 5 Milling 15 15 10-15 10-15 10-15 5-10 5-105-10 Turning 15 15 10-15 10-15 10-15 10 10 5-10 Sawing 15 15 15 15 15 1010 5-10 Honing 15 15 15 15 15 10 10 5-10 Grinding 15 15 15 15 15 10 105-10

Tablet 1 is based on diluting a concentrate of the present disclosurewith water. For example, when the desired operation is broaching withbronze, a dilution of the concentrate of the present disclosure with10-15 parts water is recommended.

For example, utilizing a concentrate having 18 wt % sodium dodecylbenzene sulfonate, 9 wt % cocamidopropyl betaine, 8 wt % hydroxyethylcellulose, 5 wt % sodium laureth sulfate, 4 wt % calcium chloride, 2 wt% ethylene glycol butyl ether and 54 wt % water, this is diluted times10 with water. Anti-rust agent is added at 1.5 ×the concentrate/10000ppm based on 1:150 ratio mix. De-foaming agent is added at 0.15 ×theconcentrate/1000 ppm based on 1:150 ratio mix. Colouring agent is addedat 0.0000095 ×the concentrate (litres)/10 ppm of 1:150 ratio mix. Theanti-rust agent is based on 1% of fully dilution of the concentrate(1:150 ratio mix). The de-foaming agent is based on 0.01% of fullydilution of the concentrate (1:150 ratio mix). An antibacterial agentmay optionally be added.

The efficacy of the metal cutting fluid concentrations and compositionsof the present disclosure may be evaluated by one or more test methodsthat indicate the effectiveness of the composition during a metalcutting operation.

For example, a vibration test was performed, comparing a cutting fluidcomposition as described in Example 11, to a commercial emulsion oil.The cutting occurred during a milling operation at a blade movement of3,000 rotations per minute, and 250 mm/min. Along the x axle, thevibration was measured to be 0.08179268 for a commercial emulsion oil,vs. 0.056828924 for the metal cutting fluid of Example 11, for a 30.5%decrease in vibration amplitude. Along the y axle, the vibration wasmeasured to be 0.07328386 for the same commercial emulsion oil, vs.0.044023185 for the metal cutting fluid of Example 11, for a 39.9%decrease in vibration amplitude. Along the z axle, the vibration wasmeasured to be 0.077851914 for the same commercial emulsion oil, vs.0.059323387 for the metal cutting fluid of Example 11, for a 23.8decrease in vibration amplitude.

When a roughness test was performed using a milling operation on mediumcarbon steel, a commercial emulsion oil provided a roughness of 4.972 asthe average R_(max) (μm), while the metal cutting fluid of Example 11provided a roughness of 3.913 R_(max) (μm). Thus, the metal cuttingfluid of the present disclosure provided a 21.3% decrease in theroughness of the cut part compared to a commercial emulsion based oil.

Example 12

As shown in Table 1, a 5 to 15-fold dilution of a material fabricationconcentrate of the present disclosure is suitably used for a largevariety of metal and other machining operations. In one embodiment, thepresent disclosure provides compositions resulting from 5 to 15 folddilution of a concentrate of the present disclosure. In one embodiment,the present disclosure provides compositions resulting from a 5-folddilution of a concentrate of the present disclosure. In anotherembodiment, the present disclosure provides compositions resulting froma 15-fold dilution of a concentrate of the present disclosure.

In one embodiment, the present disclosure provides a compositionresulting from a 10-fold dilution of a concentrate of the presentdisclosure. This composition has 0.2 wt % of sodium dodecylbenzenesulfonte, 0.05 wt % sodium laureth sulfate, 0.09 wt % cocamidopropylbetaine, 0.08 wt % hydroxyethyl cellulose, 0.04 wt % calcium chloride,0.02 wt % ethylene glycol butyl ether. To this diluted solution is addedanti-rust agent to a 0.2 wt % amount and defoaming agent to a 0.1 wt %amount.

This composition can be used in each of the machinery operationsidentified in Table 1, i.e., broaching, tapping, hobbing, cutting,drilling, milling, turning, sawing, honing or grinding of any ofaluminum (Al) alloy, brass, casting iron (also known as cast iron),bronze, low carbon steel, stainless steel, alloy steel and titanium (Ti)alloy.

Any of the various embodiments described above can be combined toprovide further embodiments. All of the U.S. patents, U.S. patentapplication publications, U.S. patent applications, foreign patents,foreign patent applications and non-patent publications referred to inthis specification and/or listed in the Application Data Sheet areincorporated herein by reference, in their entirety. Aspects of theembodiments can be modified, if necessary to employ concepts of thevarious patents, applications and publications to provide yet furtherembodiments. These and other changes can be made to the embodiments inlight of the above-detailed description. In general, in the followingclaims, the terms used should not be construed to limit the claims tothe specific embodiments disclosed in the specification and the claims,but should be construed to include all possible embodiments along withthe full scope of equivalents to which such claims are entitled.Accordingly, the claims are not limited by the disclosure.

What is claimed is:
 1. A fabrication fluid composition comprising water,a first surfactant, a thickening agent, and an anti-rust agent.
 2. Afabrication fluid composition comprising water, a first surfactant, aninorganic salt, and an anti-rust agent.
 3. A composition of claim 1 or 2wherein the first surfactant is an anionic surfactant.
 4. A compositionof claim 3 wherein the first surfactant is an anionic surfactantcomprising a sulfonate group or comprising a sulfate group.
 5. Acomposition claim 3 wherein the first surfactant is sodiumdodecylbenzene sulfonate.
 6. A composition of claim 3 wherein the firstsurfactant is sodium laureth sulfate.
 7. A composition of claim 1 or 2wherein the first surfactant is an amphoteric surfactant.
 8. Acomposition of claim 7 wherein the amphoteric surfactant comprises abetaine group.
 9. A composition claim 7 wherein the first surfactant iscocamidopropyl betaine.
 10. A composition of claim 1 or 2 comprising twosurfactants, each of the two surfactants being an anionic surfactant.11. A composition of claim 10 wherein the two surfactants are asulfate-containing surfactant and a sulfonate-containing surfactant. 12.A composition of claim 10 wherein the two surfactants are sodium laurethsulfate and sodium dodecylbenzene sulfonate.
 13. A composition of claim1 or 2 comprising two surfactants, one being an anionic surfactant andthe other being an amphoteric surfactant.
 14. A composition of claim 13wherein the two surfactants are a sulfate-containing anionic surfactantand a betaine-containing amphoteric surfactant.
 15. A composition ofclaim 14 wherein the sulfate-containing anionic surfactant is sodiumlaureth sulfate and the betaine-containing amphoteric surfactant iscocamidopropyl betaine.
 16. A composition of claim 13 wherein the twosurfactants are a sulfonate-containing anionic surfactant and abetaine-containing amphoteric surfactant.
 17. A composition of claim 16wherein the sulfonate-containing anionic surfactant is sodiumdodecylbenzene sulfonate and the betaine-containing amphotericsurfactant is cocamidopropyl betaine.
 18. A composition of claim 1 or 2comprising three surfactants, two of the three surfactants beingnon-identical anionic surfactants and one of the three surfactants beingan amphoteric surfactant.
 19. A composition of claim 18 wherein thethree surfactants are a sulfate-containing surfactant, asulfonate-containing surfactant, and a betaine-containing surfactant.20. A composition of claim 19 wherein the three surfactants are sodiumdodecylbenzene sulfonate, sodium laureth sulfate, and cocamidopropylbetaine.
 21. A composition of claim 1 or 2 wherein the anti-rust agentis sodium nitrite.
 22. A composition of claim 20 wherein the anti-rustagent is sodium nitrite.
 23. A composition of claim 1 or 2 comprising athickening agent which is a cellulosic thickening agent.
 24. Acomposition of claim 23 wherein the cellulosic thickening agent ishydroxyl ethyl cellulose.
 25. A composition of claim 20 comprising athickening agent which is a cellulosic thickening agent.
 26. Acomposition of claim 25 wherein the cellulosic thickening agent ishydroxyl ethyl cellulose.
 27. A composition of claim 1 or 2 comprisingan inorganic salt which is calcium chloride.
 28. A composition of claim20 comprising an inorganic salt.
 29. A composition of claim 28 whereinthe inorganic salt is calcium chloride
 30. A composition of claim 1 or 2comprising a defoaming agent.
 31. A composition of claim 30 wherein thedefoaming agent is a silicone polymer.
 32. A composition of claim 20comprising a defoaming agent.
 33. A composition of claim 32 wherein thedefoaming agent is a silicone polymer.
 34. A composition of claim 20comprising one or more of a cellulosic thickening agent, an inorganicsalt, and a defoaming agent.
 35. A composition of claim 20 comprising acellulosic thickening agent, an inorganic salt, and a defoaming agent.36. A composition of claim 1 comprising water, sodium dodecylbenzenesulfonate, sodium laureth sulfate, cocamidopropyl betaine, a thickeningagent such as a cellulosic thickening agent, and an anti-rust agent. 37.A composition of claim 2 comprising water, sodium dodecylbenzenesulfonate, sodium laureth sulfate, cocamidopropyl betaine, an inorganicsalt such as calcium chloride, and an anti-rust agent.
 38. A method ofmachining a material selected from metal, stone, glass and plastic,comprising applying a composition comprising a composition of any ofclaim 1-37 to a piece of material being machined, in an amount and timethat are effective to dissipate heat from the material being machined.39. The method of claim 38 wherein the material being machined is ametal selected from aluminum alloy, brass, casting iron, bronze,low-carbon steel, stainless steel, alloy steel, and titanium alloy. 40.The method of claim 38 wherein the material being machined is stone. 41.The material of claim 38 wherein the material being machined is plastic.42. The material of claim 38 wherein the material is glass.
 43. Themethod of claim 38 wherein the piece of material being machined is beingsubjected to a process selected from broaching, tapping, hobbing,cutting, drilling, milling, turning, sawing, honing, and grinding.